CYCLOMETALATED TRANSITION METAL DYES

This application claims the benefit of priority from U.S. Provisional patent application Serial No. 61/486,054 filed May 13, 2011 , and Canadian Patent

Application No. 2,774,511 filed April 17, 2012. FIELD OF THE INVENTION

The present invention relates to metal complexes, methods of preparing same, and their use in a variety of electric and photoelectric devices such as dye-sensitized solar cells (DSSC), organic light-emitting diodes (OLED), organic field effect transistors (OFET) and photoelectrochemical (PEC) cells. BACKGROUND

The dye-sensitized solar cell (DSSC) ^1,2 has attracted significant attention as a potential alternative to crystalline-silicon and thin-film devices for urban and indoor applications on account of the low embodied energy and high power-conversion efficiency (η) over disparate light intensities and relative indifference to the angle and intensity of the incident light. ^,3,4

A DSSC consists of two conducting transparent electrodes separated by an electrolyte. The anode is coated with a thin semiconducting layer such as Ti0 ₂ with which a light-absorbing dye is associated. This dye is generally composed of a metal- based complex, commonly a metal ion having polypyridine ligands bound thereto.

Photons striking the dye generally initiate a metal-to-ligand charge transfer

(MLCT). The charge is then transferred from the ligand to the semiconducting layer, and from the semiconductor to the anode. The electrolyte restores the charge of the metal complex, and also receives electrons from the cathode. Thus, an electrical current is produced.

A particularly attractive feature of the DSSC is that the light absorption and charge-transport processes ^5"7 are becoming better understood and efficiency and stability gains through changes to molecular components continue to be made. ^8"14 The performance and efficiency of the DSSC as a whole depends greatly on the performance of the dye. The ideal dye should absorb a wide spectrum of light and have redox potentials appropriately matched to the semiconductor and electrolyte for electron-injection and regeneration.

Much research effort has been spent on improving the performance of the dye since Gratzel et al. (J. Am. Chem. Soc. 1993, 115, 6382 - 6390) ¹⁵ first proposed Ru(dcbpyH ₂ )2(NCS) ₂ (dcbpyH ₂ = 4,4'-dicarboxy-2,2'-bipyridine) as the prototypical dye. A significant portion of this research has been involved in the development of a variety of ligands to improve the stability and efficiency of the dye. More recently, Bomben et al. {Inorg. Chem. 2009, 48, 9644-9652) ¹⁶ disclosed a dye that replaced the NCS ^" ligands, which are known to be relatively labile, with a cyclometalating phenylpyridine ligand (2-phenylpyridine), resulting in a more stable dye with an absorption profile that was shifted closer to the infrared region. Replacing the labile monodentate NCS ligands with chelating cyclometalating ligands also provides the opportunity to utilize the chelate effect to potentially gain control of the HOMO energy level through modification of the anionic ring. ^{17 8} Gratzel et al. (J. Am. Chem. Soc. 2009, 131 , 5930-5934) ¹⁹ disclosed a family of cyclometalating phenylpyridine ligands with halogen substituents (such as 2-(2,4-difluorophenyl) pyridine)) that resulted in a highly efficient dye.

SUMMARY

In a first embodiment of the invention there is provided a compound shown by formula (I):

wherein M is an element belonging to Group 6, Group 8, Group 9, Group 10 or Group 1 1 of the long-form Periodic Table; each R is a carboxyl, a hydroxyl, a phosphonate, a sulfonate, an alkyl group that may be an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both; each R ² is an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both; n is an integer from 1 to 4; each R ³ is selected from the group consisting of (i) an electron-withdrawing group excluding halogen atoms, (ii) a conjugated aromatic group, and (iii) combinations thereof; m is an integer from 0 to 4; and each R ⁴ is an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both. In a preferred aspect of the compound of formula (I), both R are carboxyl groups, both R ² are carboxyl groups, n is 1 , and R ³ is selected from the group consisting of N0 ₂ , CF ₃ , CN, COH, 4-pyridine, phenyl, and thiophene-2-(R ⁶ ), wherein R ⁶ is an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both.

In a second embodiment, the invention is a compound of formula (I):

wherein,

(i) M is a transition metal belonging to Group 6, Group 8, Group 9, Group 10 or Group 11 of the long-form Periodic Table;

(ii) each R ¹ is, independently of the other R , a carboxyl, a hydroxyl, a

phosphonate or a sulfonate;

and

(iii) (a) m is 0, 1 , 2, 3 or 4, and each R ² and R ⁴ is, independently of each other, selected from the group consisting of:

cyano;

halogen;

hydroxyl;

nitro;

thiol;

amino;

formyl;

amido;

alkyl, optionally substituted with any one or more of cyano, halogen,

hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyioxy, cycloalkylcarbonyloxy, heterocycloalkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkenyl, optionally substituted with any one or more of cyano, halogen,

hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyioxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkynyl, optionally substituted with any one or more of cyano, halogen,

hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulflnyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

aryl or heteroaryl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulflnyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloa!kylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkoxy, optionally substituted with any one or more of cyano, halogen,

hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkoxy or heterocycloalkyoxy or aryloxy or heteroaryloxy, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl,

cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, aikynylsulfinyi, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl,

heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl,

heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl,

heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylthio or alkenylthio or alkynylthio, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, aikynylsulfinyi, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylthio or heterocycloalkylthio or arylthio or heteroarylthio, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl,

cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl,

heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl,

heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl,

heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylsulfinyl or alkenylsulfinyl or alkynylsulfinyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylsulfinyl or heterocycloalkylsulfinyl or arylsulfinyl or

heteroarylsulfinyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylsulfonyl or alkenylsulfonyl or alkynylsulfonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloaminocarbonyl, alkenylamlnocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylsulfonyl or heterocycloalkylsulfonyl or arylsulfonyl or

heteroarylsulfonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylamlnocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylcarbonyl or alkenylcarbonyl or alkynylcarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylcarbonyl or heterocycloalkylcarbonyl or heteroarylcarbonyl,

optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl,

heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl,

arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloaminocarbonyi, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkoxycarbonyl, optionally substituted with any one or more of cyano,

halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyi, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkoxycarbonyl or heterocycloalkoxycarbonyl or aryloxycarbonyl or heteroaryloxycarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylcarbonyloxy or alkenylcarbonyloxy or alkynylcarbonyloxy, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy,

heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl,

heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl,

heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl,

heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylcarbonyloxy or heterocycloalkylcarbonyloxy or arylcarbonyloxy or heteroarylcarbonyloxy, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylamino or dialkylamino or alkenylamino or alkynylamino, optionally

substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy,

heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl,

heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl,

heteroarylcarbonyl, alkyloxyoarbonyl, cycloalkoxycarbonyl,

heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylamino or heterocycloalkylamino or arylamino or heteroarylamino, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl,

heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxyoarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylcarbonylamino or alkenylcarbonylamino or alkynylcarbonylamino,

optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl,

heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl,

heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl,

heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkycarbonylamino or heterocycloalkylcarbonylamino or

arylcarbonylamino or heteroarylcarbonylamino, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl,

heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl,

heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl,

heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylaminocarbonyl or dialkylaminocarbonyl or alkenylaminocarbonyl or alkynylaminocarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylaminocarbonyl or heterocycloaminocarbonyl or arylaminocarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl,

heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl,

cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl,

alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl,

cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy,

heteroarylcarbonyloxy, alkylamino, cycloalkylamino,

heterocycloalkylamino, alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl,

heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

-R ^a R ^b NR ^c R ^d wherein:

R ^a is arylene or heteroarylene or alkylene or alkenylene or alkynylene; R ^b is a bond, arylene, heteroarylene, alkylene, alkenylene or alkynylene; R ^c and R ^d are independently of each other aryl, heteroaryl, alkyl, alkenyl or alkynyl, and

R ^c and R ^d are, optionally and independently up to twice substituted with any one or more of:

optionally halogen-substituted:

alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, and heteroaryloxy; and wherein each of R ^a , R ^b , R° and R ^d is selected independently of the other; and

n is 1 , 2, 3 or 4, and R ³ is -CX ₂ R ^A and each R ³ is selected independently of each other, wherein:

each X is independently any halogen, and

R ^A is selected from the group consisting of:

hydrogen,

halogen;

alkyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkenyl, optionally substituted with any one or more of cyano,

halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkynyl, optionally substituted with any one or more of cyano,

halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloaikoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

ryl or heteroaryl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyi, heterocycloalkyi, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloaikoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkoxy, optionally substituted with any one or more of cyano,

halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkoxy or heterocycloalkyoxy or aryloxy or heteroaryloxy,

optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylthio or alkenylthio or alkynylthio, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylthio or heterocycloalkylthio or arylthio or heteroarylthio, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylsulfinyl or alkenylsulfinyl or alkynylsulfinyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyi, heterocycloalkyi, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylsulfinyl or heterocycloalkylsulfinyl or arylsulfinyl or

heteroarylsulfinyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylsulfonyl or alkenylsulfonyl or alkynylsulfonyl, optionally

substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl,

heterocycloalkyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroary!thio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylsulfonyl or heterocycloalkylsulfonyl or arylsulfonyl or

heteroarylsulfonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyi, heterocycloalkyi, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylcarbonyl or alkenylcarbonyl or alkynylcarbonyl, optionally

substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl,

heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy,

heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio,

heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino, heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylcarbonyl or heterocycloalkylcarbonyl or heteroarylcarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycioalkylsulfinyl, alkenylsulfinyl, aikynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamlno, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkoxycarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkoxycarbonyl or heterocycloalkoxycarbonyl or aryloxycarbonyl or heteroaryloxycarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio,

heterocycloalkythio, alkenylthio, alkynylthio, arylthio,

heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylcarbonyloxy or alkenylcarbonyloxy or alkynylcarbonyloxy,

optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyi, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy,

heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cydoalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio,

heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylcarbonyloxy or heterocycloalkylcarbonyloxy or

arylcarbonyloxy or heteroarylcarbonyloxy, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl,

heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, aikylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylamino or dialkylamino or alkenylamino or alkynylamino, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyi, heterocycloalkyi, aryl, heteroaryl, alkoxy, cycloalkoxy,

heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio,

heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylamino or heterocycloalkylamino or arylamino or

heteroarylamino, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyi, heterocycloalkyi, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylcarbonylamino or alkenylcarbonylamino or

alkynylcarbonylamino, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulflnyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkycarbonylamino or heterocycloalkylcarbonylamino or

arylcarbonylamino or heteroarylcarbonylamino, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl,

heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl, alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

alkylaminocarbonyl or dialkylaminocarbonyl or alkenylaminocarbonyl or alkynylaminocarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, cycloalkyi, heterocycloalkyi, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl,

heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl, cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino,

heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl,

cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl;

cycloalkylaminocarbonyl or heterocycloaminocarbonyl or

arylaminocarbonyl, optionally substituted with any one or more of cyano, halogen, hydroxyl, nitro, thiol, amino, formyl, amido, sulfonate, alkyl, cycloalkyi, heterocycloalkyi, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylsulfinyl, cycloalkylsulfinyl, heterocycloalkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkysulfonyl, cycloalkylsulfonyl, heterocycloalkylsulfonyl, alkenysulfonyl, alkynylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, heterocycloalkylcabonyloxy, alkenylcarbonyloxy,

alkynylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkylamino, cycloalkylamino, heterocycloalkylamino,

alkenylamino, alkynylamino, arylamino, heteroarylamino, alkylcarbonylamino, cycloalkylcarbonylamino, heterocycloakylcarbonylamino, alkenylcarbonylamino,

alkynylcarbonylamino, arylcarbonylamino,

heteroarylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloaminocarbonyl,

alkenylaminocarbonyl, alkynylaminocarbonyl, arylaminocarbonyl, heteroarylcarbonyl, dialkylaminocarbonyl.

As an alternative to to the elements defined as in foregoing subparagraph (iii), said elements are defined as:

(iv) each R ² is selected independently from the group defined in (iii)(a); and

n + m = 1, 2, 3, 4, 5, 6, 7 or 8, and R ³ and R ⁴ are independently selected from the group defined in (iii)(b).

So, in a particular aspect of the second embodiment, each R ² , n, m, R ³ and R ⁴ are as defined in (iv).

In such aspect, n + m can be 1 , 2, 3 or 4, and each R ^A can be selected independently from the group consisting of:

hydrogen,

halogen,

alkyl optionally substituted as defined in (iii)(b), and

aryl optionally substituted as defined in (iii)(b), or heteroaryl optionally

substituted as defined in (iii)(b). The alkyl group of R ^A can be a linear or branched alkyl group having from 1 to 6 carbon atoms.

The aryl group of R ^A can have 6 to 14 carbon atoms, and said heteroaryl group of R ^A has 1 or 2 heteroatoms and 3 to 6 carbon atoms.

In a particular aspect of the second embodiment, n = 2 and each R ^A is the same as the other R ^A .

Each R ^A can be hydrogen, halogen, linear or branched unsubstituted alkyl.

Each R ^A and each X can be the same as each other and are halogen.

Each R ³ can be trifluoromethyl.

Each R ³ can be in a meta position with respect to the carbon atom of the C- bond of the phenyl group shown in formula (I), moreso when each R ³ is a

trifluoromethyl group.

Each R ² can be, independently of the other R ² , aryl optionally substituted as defined in (iii)(a) or heteroaryl optionally substituted as defined in (iii)(a).

Each R ² can be, independently of the other R ² , heteroaryl selected from the group consisting of:

(pyrollyl, furanyl, thiophenyl, selenophenyl, phosphole), the heteroaryl being optionally substituted as defined in (iii)(a).

Each R ² can be, independently of the other R ² , 5-substituted pyrollyl, 5- substituted furanyl, 5-substituted thiophenyl, 5-substituted selenophenyl, or 5- substituted phosphole.

The heteroaryl substitution of each R ² can be, independently of the other R ² , selected from the group consisting of halogen, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, heteroaryloxy, alkylthio, cycloalkylthio, heterocycloalkythio, alkenylthio, alkynylthio, arylthio, heteroarylthio, alkylcarbonyl, cycloalkylcarbonyl, heterocycloalkylcarbonyl, alkenylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkyloxycarbonyl,

cycloalkoxycarbonyl, heterocycloalkoxycarbonyl, aryloxycarbonyl,

heteroaryloxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy,

heterocycloalkylcabonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, arylcarbonyloxy, and heteroarylcarbonyloxy. Each R ² can be the same as the other R and the heteroaryl substitution can be alkyl.

Each R ² can be, independently of the other R ² , -R ^a R NR ^c R ^d as defined in

(iii)(a).

Each R ^a can be, independently of the other R ^a , heteroarylene.

Each R ^b can be, independently of the other R ^b , arylene.

Each of R ^c and R ^d can be, independently of each other, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, cycloalkoxy, or aryloxy.

Each R ^a can be the same as the other R ^a with each R ^b the same as the other R ^b , and R and R ^d the same as each other.

R ^a can be selected from the group:

R ^b can be

Each of R ^c and R ^d can be alkoxy having 2 to 20 carbon atoms.

Each of R° and R ^d can be -0(CH ₂ ) ₅ CH ₃ .

In a third embodiment, a compound of the invention has formula (I):

wherein M is an element belonging to Group 6, Group 8, Group 9, Group 10 or Group 11 of the long-form Periodic Table;

each R is selected from the group consisting of a carboxyl, a hydroxyl, a

phosphonate, a sulfonate;

each R ² is an aromatic group that may be substituted; each R ³ is an electron-withdrawing group and n is an integer from 1 to 4; and each R ⁴ is an alkyl group that may be substituted and m is an integer from 0 to 4.

Each R ¹ can be a carboxylate.

Each R ² can be the same as each other R ² .

Each R ³ can be selected from the group consisting of NO ₂ , CF ₃ , CN, COH, 4- pyridine, phenyl, thiophene-2-(R ⁶ ).

R ³ can be CF ₃ .

The value of n is 2 in a particular aspect.

R ⁴ can be CF ₃ .

The value of m is 2 in a particular aspect, or m can be 0.

In a particular aspect, a compound of the invention has the stereochemical orientation of formula (VI):

In a fourth embodiment, the invention is compound shown by formula (VII):

(VII) wherein M is an element belonging to Group 6, Group 8, Group 9, Group 10 or Group 11 of the long-form Periodic Table; each R ¹ is selected from the group consisting of a carboxyl, a hydroxyl, a phosphate, a sulfonate, an alkyl group that may be substituted, an aromatic group that may be substituted, salts thereof, and combinations thereof; each R ² is selected from the group consisting of a carboxyl, a hydroxyl, a phosphate, a sulfonate, an alkyl group that may be substituted, an aromatic group that may be substituted, salts thereof, and combinations thereof; n is an integer from 1 to 4; each R ³ is selected from the group consisting of (i) an electron-withdrawing group that is not a halogen atom, (ii) a conjugated aromatic group, and (iii) combinations thereof; m is an integer from 0 to 4; and each R ⁴ is an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both.

Each R ¹ can be selected to be a group capable of associating with a semiconducting material.

The value of n can be 1 , and R ³ can be selected from the group consisting of N0 ₂ , CF ₃ , CN, COH, 4-pyridine, phenyl, and thiophene-2-(R ⁶ ), wherein R ⁶ is an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both. In particular aspect, m is 0, and R is carbaldehyde.

Each R ¹ can be selected from the group consisting of COOH, P0 ₃ H, C=C(COOH)CN, C=C(COOH)COOH, S0 ₃ H, and their corresponding deprotonated forms.

According to fifth embodiment, the invention is a compound shown by formula (VII):

(VII) wherein M is an element belonging to Group 6, Group 8, Group 9, Group 10 or Group 11 of the long-form Periodic Table; each R ¹ is selected from the group consisting of a carboxyl, a hydroxyl, a phosphate, a sulfonate, an alkyl group that may be substituted, an aromatic group that may be substituted, salts thereof, and combinations thereof; each R ² is selected from the group consisting of a carboxyl, a hydroxyl, a phosphate, a sulfonate, an alkyl group that may be substituted, an aromatic group that may be substituted, salts thereof, and combinations thereof, n is an integer from 1 to 4; each R ³ is selected from the group consisting of (i) an electron-withdrawing group that is not a halogen atom, 4-pyridine, phenyl, H0 ₂ , or thiophene-2-(carbaldehyde) (ii) a conjugated aromatic group, and (iii) combinations thereof; m is an integer from 0 to 4; and each R ⁴ is an alkyl group that may be substituted, an aromatic group that may be substituted, or a combination of both. Each R ¹ can be a group capable of associating with a semiconducting material. Each R ² can be a group capable of associating with a semiconducting material. The value of n can be , and R ³ can be selected from the group consisting of CF ₃ , CN, and COH.

Each R can be selected from the group consisting of COOH, P0 ₃ H,

C=C(COOH)CN, C=C(COOH)COOH, S0 ₃ H, and their corresponding deprotonated forms.

is typically selected from the group consisting of iron, ruthenium, osmium, cobalt, indium, palladium, platinum, and chromium.

Preferably, M is ruthenium.

In the foregoing description of compounds of the invention, it is possible for a compound to exist in a variety of salt forms. For example, when R is a carboxyl, the carboxyl may be in a protonated or unprotonated form e.g., -CO2H or -(CO2XNBU4). Unless otherwise specified, such salt forms of a compound are intended to be covered by the description of the compound given herein.

An aspect of the invention is a photoelectric device comprising a first electrode, a second electrode, and an electrolyte deposited in electrical communication with said first and second electrodes, wherein the first electrode comprises a compound of the invention.

The compound can be deposited on a surface of the first electrode.

The first electrode can further comprise a semiconductor layer wherein the compound is deposited on a surface of the semiconductor layer.

The first electrode can comprise a substrate, wherein the semiconductor layer is deposited on a surface of the substrate.

The substrate can comprise an electrically conductive material.

The substrate can be selected from the group consisting of transparent glass and sheet metal.

In a preferred aspect, the photoelectric device is a dye-sensitized solar cell, and the compound is incorporated thereinto in an amount sufficient to obtain a power conversion efficiency of greater than 3% when exposed to simulated sunlight of an intensity of 1 Sun under AM1.5 conditions.

The photoelectric device can have power conversion efficiency that is at least 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% or 18%.

In a preferred aspect, electrolyte of a photoelectric device is a single electron redox shuttle. Preferably here, a compound of the invention is a second embodiment compound.

In a preferred aspect, the electrolyte is an iron (Fe ^IM /Fe")- or a cobalt (Co"VCo")- based electrolyte.

The semiconductor can comprise an oxide e.g., ΤΊΟ2 and a surface of the semiconductor can be free of an insulating oxide blocking layer to permit direct contact of the compound and the surface. Such an electrolyte can be substantially free of halogen electrolytes. By "substantially free" of halogen in this context is meant that there is no halogen present in the electrolyte solution but if some is present it is present in a sufficiently small amount that it does not participate in the redox chemistry that reduces the photooxidized dye.

A photoelectric device can be an organic light-emitting diode.

In another aspect, the invention is an electrode for use in a photoelectric device formed by contacting a semiconductor layer deposited on a surface of a substrate with a solution comprising a compound of the invention wherein the compound is associated with the semiconductor layer.

The substrate can comprise an electrically conductive material.

The substrate can be selected from the group consisting of transparent glass and sheet metal.

The invention includes a method for the manufacture of a photoelectric device comprising contacting an electrode comprising a semiconductor layer deposited on a surface of a substrate with a solution comprising a compound of the invention, thereby causing the compound to be associated with the semiconductor layer.

The invention is also an organic field effect transistor comprising a compound of the invention.

In yet another aspect, the invention is a photoelectrochemical cell comprising aompound of the invention.

In a preferred aspect of the photoelectric device, the photoelectric device is a dye-sensitized solar cell (DSSC).

In another preferred aspect of the photoelectric device, the photoelectric device is an organic light-emitting diode (OLED), wherein the first electrode further comprises the compound according to the invention deposited on a surface of an electrically conductive substrate such as transparent glass or sheet metal. In another aspect of the invention, there is provided a photoelectrochemical cell comprising the compound according to the invention, wherein the compound is used as a light absorber to separate water into hydrogen and oxygen.

In another aspect of the invention, there is provided field effect transistor comprising the compound according to the invention, wherein the compound is used as a bistable redox component.

A further understanding of the functional and advantageous aspects of the disclosure can be realized by reference to the following detailed description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

Particular embodiments will now be described, by way of example only, with reference to the drawings, in which:

Figure 1 is a schematic of the synthesis of compounds 1 (R ¹ = R ² = R ³ = R ⁴ = H); 2 (R = N0 ₂ , and R ² = R ³ = R ⁴ = H); 3 (R ¹ = H, R ² = N0 ₂ , and R ³ = R ⁴ = H); 4 (R = R ² = H, R ³ = N0 ₂ , and R ⁴ = H); 5 (R ¹ = N0 ₂ , R ² = H, R ³ = N0 ₂ , and R ⁴ = H); 6 (R ¹ = F, R2 = H, R ³ = F, and R ⁴ = H); 7 (R = H, R ² = phenyl, and R ³ = R ⁴ = H); 8 (R ¹ = H, R ² = 4-pyridyl, and R ³ = R ⁴ = H); 9 (R = H, R ² = thiophene-2-carbaldehyde, and R ³ = R ⁴ = H);

Figure 2(a) is a graph depicting electronic absorption spectra of compounds 1- 5 of Example 1 ;

Figure 2b is a graph depicting electronic absorption spectra of the compounds 1a, 7a-9a from Example 1;

Figure 3 is a graph depicting an energy level diagram showing the dominant transitions that comprise the lowest-energy absorption band A _max i for compounds 3, 7, and 9 from Example 1 , wherein transitions that are predicted to contribute less than 10% to the absorbance band are omitted;

Figure 4 is a schematic depicting a dye-sensitized solar cell design;

Figure 5 depicts the structures of compounds 1 ([Ru(dcbpyH ₂ ) ₂ (L1 )]PF ₆ ); 1a ((Bu ₄ N) ₃ [Ru(dcbpy)(dcbpyH)(L1)]PF ₆ ); 2 ([Ru(dcbpyH ₂ ) ₂ (L2)]PF ₆ ); 3

<[Ru(dcbpyH ₂ ) ₂ (L3)jPF ₆ ); 3a ((Bu ₄ N) ₄ [Ru(dcbpy) ₂ (L3)]PF ₆ ); 4

([Ru(dcbpyH ₂ ) ₂ (L4)]PF ₆ ); 5 ([Ru(dcbpyH ₂ ) ₂ (L5)]PF ₆ ); 7 ([Ru(dcbpyH ₂ )(dcbpyH)(L7)]); 7a ((Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L7)]); 8 ([Ru(dcbpyH ₂ ) ₂ (L8-H)]); 8a ((Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L8)]); 9 ([Ru(dcbpyH ₂ )(dcbpyH)(L9)]); and 9a ((Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L9)]);

Figure 6 shows the synthetic scheme for synthesis of compound 10. Figure 7 is a UV/Vis spectra for MeOH solutions of compounds 10, 11 , and 12; the emission spectrum of 10 (A _ex =555 nm) is also provided;

Figure 8 is the absorbance on Ti0 ₂ for compounds 10, 11 , and 12;

Figure 9 is the experimental UV-vis absorption spectrum of compound 10 overlaid with calculated transitions represented by vertical bars. The HOMO-LUMO transition (λ-ι) and four transitions (λ ₂ -λ ₅ ) corresponding to the experimental data are shown. For simplicity, only the contribution(s) greater than 30% for each oscillator are described. Details of calculated transitions (theoretical wavelength in nm, oscillator strength, percentage contribution to the transition): λι HOMO→LU O (662, 0.0079, 88%); λ ₂ , HOMO-1→LUMO (534, 0.172, 65%); λ ₃ , HOMO-1→LUMO+1 and HOMO- 2→LUMO+1 (491 , 0.018, 63% and 32%); λ ₄ , HOMO-1→LUMO+2 (428, 0.107, 70%); λ ₅ , HOMO-1→LUMO+6 (362, 0.147, 79%). The thermodynamic position of the HOMO energy level is calculated to be +0.97 V vs NHE, a deviation of 20 mV from the experimentally determined value of +0.99 V vs NHE;

Figure 10 shows the cyclic voltammogram of compound 10 recorded in a 0.1 M

Bu ₄ NBF ₄ DMF solution at a scan rate of 200 mV/s. The artifact visible at -0.6 V vs NHE is adventitious oxygen;

Figure 11 shows a) Current-voltage curves recorded under AM1.5 conditions and b) IPCE data for DSSCs sensitized with compounds 10 and 12. Squares (■) and circles (·) represent cells measured with EL1 (I7I ₃ ^" ) and EL2 (Co'"/Co"), respectively (Ti0 ₂ : 12 μπι active and 3 μηι scattering layers);

Figure 12 shows the normalized IPCE curves for compounds 10 and 12 with electrolytes EL1 and EL2. Ti0 ₂ films: 12 μιτι active layer + 3 μιη scattering layer;

Figure 13 shows the nyquist impedance plots for devices sensitized by 10 and 12 with electrolytes EL1 and EL2. Ti0 ₂ films: 12 μιη active layer + 3 μιτι scattering layer;

Figure 14 is the transmission line model employed in this study. ²⁰ R _s = cell series resistance. RJCO = resistance at the FTO/electrolyte interface. CTCO = capacitance at FTO glass/Ti0 ₂ /electrolyte interface. R _t =∑(r _t ) = transport resistance through Ti0 ₂ . R _ct =∑(r _ct ) = resistance to electron recombination with Ti0 ₂ . C _ct =∑(c _c t) = capacitance at Ti0 ₂ /electrolyte interface. Rp _t = electron transfer resistance at Pt coated counter electrode. Cp _t = capacitance at counter electrodet/electrolyte interface;

Figure 15 shows the synthetic scheme for synthesis of compound 14; Figure 16 shows structures of compounds 1 , 10, 14 and 18. The counteranion for 1 and 14 is PFe;

Figure 17 is an ORTEP plot of [Ru(bpy)(deeb)(ppy)]PF ₆ . Ellipsoids presented at 30% probability level. The isomer depicted in Figure 16 was assigned according to this crystal structure;

Figure 18 shows UV-vis absorption spectra of compounds 10, 14 and 18 recorded in DMF. Inset: Cyclic voltammagrams of 10, 14 and 18 recorded in DMF at 200 mV/s with 0.1 M NBu ₄ BF ₄ supporting electrolyte;

Figure 19 shows IPCE traces for 14 with (Entry 5, Table 4) and without chenodeoxycholic acid (Entry 6, Table 4). Inset: Jsc-V curves for 14 with (Entry 5, Table 4) and without chenodeoxycholic acid (Entry 6, Table 4);

Figure 20 shows impedance modelling (see Figure 21) of (A) R _c t (B) R _t and (C) C _ct vs V. Dashed and solid lines represent cells of 14 with and without

chenodeoxycholic acid, respectively. Dotted line represents 10 without

chenodeoxycholic acid; and

Figure 21 shows transmission line equivalent circuit employed in EIS modeling. ¹⁰

DETAILED DESCRIPTION

Various embodiments and aspects of the disclosure will be described with reference to details discussed below. The following description and drawings are illustrative of the disclosure and are not to be construed as limiting the disclosure. Numerous specific details are described to provide a thorough understanding of various embodiments of the present disclosure. However, in certain instances, well- known or conventional details are not described in order to provide a concise discussion of embodiments of the present disclosure.

As used herein, the terms, "comprises" and "comprising" are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in this specification including claims, the terms, "comprises" and "comprising" and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.

As used herein, the term "exemplary" means "serving as an example, instance, or illustration," and should not be construed as preferred or advantageous over other configurations disclosed herein. As used herein, the terms "about" and "approximately", when used in conjunction with ranges of dimensions of particles, compositions of mixtures or other physical properties or characteristics, are meant to cover slight variations that may exist in the upper and lower limits of the ranges of dimensions so as to not exclude embodiments where on average most of the dimensions are satisfied but where statistically dimensions may exist outside this region. It is not the intention to exclude embodiments such as these from the present disclosure.

As used herein, the term "dcbpyH ₂ " is used as a shorthand of group of the form 4,4'-dicarboxy-2,2'-bipyridine.

As used herein, the term "Χ ^Λ Υ" is used as a shorthand for a ligand of the form given by formula (II)

As used herein, the term 'ligand" describes an ion or a molecule that binds to a central metal atom, and formally donates one or more of its electron pairs to the metal atom.

As used herein, the term "aromatic" describes a hydrocarbon ring structure having at least three sides and alternating single and double bonds between the nodal atoms of the ring.

As used herein, the term "electrolyte" describes an electrically conductive substance containing free ions. Suitable electrolytes include solutions containing I l ₃ ^~ ions, but in certain preferred embodiments, electrolytes are other than I 1 ₃ ^" or other halogen-containing electrolytes. As described in connection with certain preferred embodiments, a preferred electrolyte is a cobalt-based (Co'"/Co") electrolyte.

As used herein, the term "electron-withdrawing group" describes substituents that draw electrons away from the center of the molecule to which they belong.

In another aspect of the invention, M is ruthenium, both R ¹ are carboxyl groups, R ² are carboxyl groups, n is 1 , R ³ is a phenyl group and m is 0, resulting in a compound (herein referred to as compound 7) of the form shown by formula (III):

In another aspect, the compound of formula (I), M is ruthenium, both R are carboxyl groups, both R ² are carboxyl groups, n is 1 , R ³ is a 4-pyridine group, and m is 0 resulting in a compound (herein referred to as compound 8) of the form shown by formula (IV):

In another aspect, , M of formula (I) is ruthenium, both R are carboxyl groups, both R ² are carboxyl groups, n is 1 , R ³ is a thiophene-2-carbaldehyde group, and m is 0 resulting in a compound (herein referred to as compound 9) of the form shown by formula (V):

This scenario is one possible optimal configuration because the electron- withdrawing R ³ group results in an expansion of the HOMO over the R ³ substituent, leading to a series of broad absorption bands in the visible region of the spectrum, arising primarily from mixed-metal/ligand-to-ligand charge-transfer transitions.

The central ion in the complex compound may be any element belonging to Group 6, Group 8, Group 9, Group 10, or Group 1 1 of the long-form Periodic Table. Preferred elements are iron, ruthenium, osmium, iridium, cobalt, palladium, platinum, and chromium. In a preferred aspect, the element is ruthenium.

Unless stated otherwise, the stereochemical orientation of the ligands of compounds (I) to (V) is not implied by their representations herein.

In an aspect, the invention is a complex having the stereochemical structure of formula (VI):

This invention may also be said broadly to be composed of the parts, elements and features referred to or indicated herein, individually or collectively, in their various possible combinations. It is to be understood that those combinations and/or subcombinations. So, for example, a compound in which M = Ru, each R ¹ is a phosphonate, m = 0, n = 2 and each R ³ is a trifluoromethyl group in a meta position with respect to the point of attachment of the phenyl group to Ru is described as though explicitly described in the foregoing description. Likewise, ranges and subranges are described as though each is explicitly described herein. For example, formula (I) includes the possibility of one or more alkynyl groups in which each of such groups includes 2 to 10 carbon atoms. This disclosure thus includes such compounds in which an alkynyl group has 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbons, and includes groups of compounds defined by carbon atom ranges e.g., an alkynyl group having from 3 to 7 atoms.

"Halo" or "halogen" refers to a substituent fluorine, chlorine, bromine or iodine. The term "hydroxyl" refers to -OH. The term "amino" denotes the -NH2 group.

The term "formyl" refers to -C(0)H. This group is also referred to as a

"carbaldehyde" group.

"Amido" refers to -C(0)NH ₂ .

"Thiol" refers to -SH.

The term "carboxyl" refers to functional group -CO2H and deprotonated forms and salts thereof.

"Alkyl" includes hydrocarbon structures having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms and more preferably 1 to 8 carbon atoms or 1 to 6 carbon atoms, or more suitably 1 to 4 carbon atoms. An alkyl group can have 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, or any range of carbon atoms defined by these numbers e.g., 2 to 6 carbon atoms. An alkyl group or radical may be "linear alkyl" or "branched alkyl". For any use of the term "alkyl", unless clearly indicated otherwise, it is intended to embrace all variations of alkyl groups disclosed herein, as measured by the number of carbon atoms, the same as if each and every alkyl group were explicitly and individually listed for each usage of the term. When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are included, so, for example, "butyl" is includes n-butyl, sec-butyl, iso-butyl and t-butyl. Suitable alkyls include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl and hexyl. This definition of alkyl extends to an alkyl group as it may occur when the alkyl group is part of another molecular moiety, for example, a "perhaloalkyl", or a heteroaryl optionally substituted with an alkyl, or an alkoxy group, a dialkylamino group, etc.

A "perhaloalkyl" group is a perhaloalkyl group such as the residue -CF ₃ ,

-CF2CF3, -CCI2CCI2CCI3, etc.

When an alkyl group is cyclic, it is referred to as a "cycloalkyl" group and has 3 to 20 annular carbon atoms, preferably 3 to 12 annular carbon atoms and more preferably 3 to 8 or 3, 4, 5 or 6 annular carbon atoms. A cycloalkyl group can have 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, or any range of carbon atoms defined by these numbers e.g., 5 to 8 carbon atoms.Suitable cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "heterocycloalkyl" indicates a cycloalkyl radical containing 1 to 19 carbon atoms in which one or more of the carbon atoms is replaced by a

corresponding one or more heteroatoms. Generally, the number of heteroatoms included in the ring is 1 to 6 heteroatoms (O, S, N), preferably 1 , 2, or 3 heteroatoms. The radical is attached to the parent structure to a carbon atom of the ring.

"Alkenyl" is a hydrocarbon group of 2 to 20 carbon atoms, branched or linear, or it can 2 to 10 carbon atoms and more preferably 2 to 6 carbon atoms, and the group has at least 1 and up to 3 sites of alkenyl unsaturation.

"Alkynyl" is a hydrocarbon group having 2 to 20 carbon atoms, branched or linear, that contains an unsaturation i.e., a -C=C- moiety, and preferably having from 2 to 10 carbon atoms and more preferably 3 to 6 carbon atoms.

The term "aryl" indicates an aromatic monocyclic or multicyclic ring system containing 6 to 20 carbon atoms or 6 to 14 carbon atoms, and preferably about 6 to about 10 carbon atoms. The rings can be fused carbocyclic rings with at least one aromatic ring, such as phenyl, naphthyl, indenyl and indanyl.

The term "heteroaryl" indicates a radical of one or more heterocyclic aromatic rings containing 1 to 6 heteroatoms (oxygen, sulfur, nitrogen, selenium, phosphine) and 3 to 20 carbon atoms, such as 1 to 5 heteroatoms and 1 to 10 carbon atoms, such as 1 to 5 heteroatoms and 1 to 6 carbon atoms, such as 1 to 5 heteroatoms and 1 to 3 carbon atoms, in particular 5- or 6-membered rings with 1 to 4 heteroatoms or optionally fused bicyclic rings with 1 to 4 heteroatoms, and wherein at least one ring is aromatic, e.g. pyridyl, quinolyl, isoquinolyl, indolyl, tetrazolyl, thiazolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thienyl (radical obtained by removal of hydrogen from the ring of thiophene), selenophenyl, pyrazinyl, isothiazolyl, benzimidazolyl and benzofuranyl.

"Alkoxy" is an alkyl group that is connected to the parent structure through an oxygen atom (-O-alkyl). Examples include methoxy, ethoxy, propoxy and isopropoxy. When a cycloalkyl radical is connected to the parent structure through an oxygen atom, the group is referred to as a "cycloalkoxy" group. Examples include

cyclopropyloxy and cyclohexyloxy. When a heterocycloalkyl radical is connected to the parent structure through an oxygen atom, the group is referred to as a

"heterocycloalkoxy" group.

A "perhaloalkoxy" is a perhaloalkyl group attached to the parent structure through an oxygen, such as the residue -OCF ₃ .

"Aryloxy" is an aryl group that is connected to the parent structure through an oxygen atom (-O-aryl), for example the residues phenoxy and naphthoxy.

When a heteroaryl radical is connected to the parent structure through an oxygen atom, the group is referred to as a "heteroaryloxy" group.

"Alkylthio" is an alkyl group that is connected to the parent structure through a sulfur atom (-S-alkyl) an example of alkylthio being -SCH2(CH ₃ ).

"Alkylsulfinyl" is an alkyl group connected to the parent structure through a S(O) moiety (-S(O)alkyl), an example being -S(0)CH ₂ CH ₃ .

"Alkylsulfonyl" is a -S(0 ₂ )alkyl group i.e., an alkyl group bound to the parent moiety through the sulfur atom of sulfonyl moiety.

An "alkylcarbonyl" group is an alkyl radical connected to the parent structure through a carbonyl linkage i.e., -C(0)R where R is an alkyl group. An example is - C(0)CH ₂ CH ₂ CH ₃ .

An "alkyloxycarbonyl" group is an alkoxy radical connected to the parent structure through a carbonyl linkage i.e., -C(0)OR where R is an alkyl group. An example is -C(0)OCH ₃ .

An "alkylcarbonyloxy" group is an alkylcarbonyl group that is connected to the parent structure through an oxygen atom i.e., -0-C(0)R where R is an alkyl group. An example is -OC(0)CH ₂ CH ₃ .

An "alkylamino" group refers to an amino group (-NH ₂ ) in which one hydrogen atom is replaced by an alkyl group i.e, -NHR where R is an alkyl group, such as in -NHCH(CH ₃ ) ₂ . Examples of alkylamino include methylamino, ethylamino, propylamino, and dodecylamino. A "dialkylamino" group is an amino group in which both hydrogen atoms are replaced by alkyl groups i.e., -NR2 where R is an alkyl group which may or may not be the same as each other. An example is -N(CH ₃ )(CH ₂ CH ₃ ).

An "alkylcarbonylamino" group is an aminogroup (-NH ₂ ) in which one hydrogen is replaced by an alkylcarbonyl radical i.e., -NHC(0)R where R is an alkyl group.

Examples of alkylcarbonylamino groups are -NHC(0)CH ₂ CH ₃ and -NHC(0)CH(CH ₃ ) ₂ . A

An "alkylaminocarbonyl" group is an alkylamino group connected to the parent structure through a carbonyl linkage i.e., -C(0)NHR where R is an alkyl group. An example is -C(0)NHCH ₂ CH ₂ CH ₃ . In a "dialkylaminocarbonyl" group, both hydrogen atoms of the amino group (-NH ₂ ) are replaced by alkyl groups which may or may not be the same as each other. An example is -C(0)N(CH ₃ )(CH ₂ CH ₃ ).

"Alkylene" is a bivalent saturated, straight or branched chain hydrocarbon structure having from 1 to 20, more preferably 1 to 10 carbon atoms, or 1 to 6 carbon atoms. Examples of alkylene groups include methylene (-CH ₂ -), ethylene, propylene, iso-propylene, n-butylene, isobutylene, and n-hexylene.

"Alkenylene" is a bivalent straight or branched chain hydrocarbon structure containing 1 to 6 carbon-carbon double bonds. The structure has from 2 to 20, more preferably 2 to 10 carbon atoms, or 2 to 6 carbon atoms. An example is

-CH ₂ CH=CHCH ₂ CH ₂ -.

"Alkynylene" is a bivalent straight or branched chain hydrocarbon group of 2 to 20, or 2 to 10, or 2 to 6 carbon atoms containing at least one carbon-carbon triple bond. Examples of alkynylene include ethynylene (-C≡C-), propynylene, and butynylene.

"Arylene" is an aryl group but for being bivalent i.e., an aryl group in which a hydrogen atom has been replaced by a bond, an example being -C6H ₄ -.

"Heteroarylene" is a heteroaryl group but for being bivalent i.e., a heteroaryl group in which a hydrogen atom bound to a carbon has been replaced by a bond, an example being

When a radical e.g., an alkyl or aryl radical is said to be "substituted", as in a halogen-substituted alkyl group, this means that one or more of the hydrogen atoms of the named radical is replaced by the indicated substituent, as in this example a halogen. Examples of halogen-substituted alkyl groups are trifluoromethyl,

difluoromethyl, flurormethyl, perfluoroethyl, etc. Unless otherwise indicated, substitutions are made independently of each other, so another example of a halogen- substituted alkyl group is -CF ₂ CI. A parent structure may also be substituted with a substituent that itself may be substituted, as in an alkyl-substituted aryl wherein the alkyl group is halogen-substituted alkyl.

Also, the meanings of other terms are provided by the above list of terms, as the skilled person would understand. For example, the meaning of the term

"arylsulfonyl" is understood. In this case, substitution for the defined term "aryl" in place of "alkyl" of the term "alkylsulfonyl" leads to the definition of "arylsulfonyl" even though the definition of this latter term is not explicitly set out. The meanings of other terms e.g., "cycloalkylthio", "heteroaryloxycarbonyl" are similarly determined.

As described above in connection with the term "alkyl", terms are also used to denote a residue as part of a larger group and when such a term is used, is taken together with other atoms to form another group. For instance, reference to - C(0)Oalkyl is an ester functional group bound to its parent functional group by the carbon atom of its carbonyl group, an example being -C(0)OCH ₃ .

It should be noted here, that when discussing radical portions of a molecule, such as a substituted phenyl group -C ₆ H ₃ R ^a R ^b connecting bonds of R ^a and R ^b may be omitted in various contexts for the sake of convenience, and the skilled person understands this.

A DSSC is shown in Figure 4. Construction of a DSSC has been previously described and would be well understood by a person skilled in the art. Briefly, the DSSC comprises and anode (10) and a cathode (20) arranged in a sandwich-like configuration. Separating the two electrodes is an electrolyte (45) and a polymer spacer (not shown) which acts to isolate the two conductive electrodes and seal in the electrolyte. Electrical connections (50) are provided on the anode (10) and the cathode (20). An example of a material from which the electrodes may be constructed is fluorine-doped tin oxide conductive glass though other materials are known to persons skilled in the art. The purpose of the electrolyte (45) is to restore the oxidation state of the light-absorbing dye and to receive electrons at the cathode (20). An example of an electrolyte is an acetonitrile solution containing iodide and triiodide, though a person skilled in the art would be aware of other electrolytic compounds that could also serve this purpose.

At the anode (10) is deposited a thin layer of semiconductor material (30). An example of a semiconductor material is titanium oxide (T1O2) though other

semiconductors may be known to a person skilled in the art. An example of the thickness of the layer of semiconductor material is about 12 μιη though other thicknesses may be known to a person skilled in the art.

A person skilled in the art would be aware of several methods by which semiconductor material may be deposited at the anode (10). An example of a method by which semiconductor material may be deposited at the anode (10) is to screen print a layer of semiconductor paste on the anode followed by sintering at elevated temperatures. After the semiconductor (30) has been deposited at the anode (10), the anode (10) may be subject to an appropriate heat treatment and further post treatments as would be understood by a person skilled in the art.

A light-absorbing dye (55) is associated with the semiconductor anode (10). One means of associating the dye (55) with the anode (10) is to immerse the heat- treated anode (10) in a dye solution for several hours such that the porous semiconductor material adsorbs the dye. An example of a concentration of dye solution suitable for adsorption is 2x10 ^' M though a person skilled in the art would be aware of other suitable concentrations. The association of the light-absorbing dye and the semiconductor is maintained through the chemical bond achieved through a condensation reaction between the anchoring group of the dye complex and the semiconductor material.

Adsorption is one method by which the light-absorbing dye (55) may be integrated, incorporated or otherwise associated with the semiconductor anode (10). Other methods for achieving association of the light-absorbing dye and the

semiconductor anode would be known to a skilled reader.

Construction of the cathode (20) is well understood by a person skilled in the art. An example of a method by which a cathode may be constructed is to drill a small hole in the non conductive side of the cathode. A small amount of platinum (for example 5-10 g/cm ² ) is deposited on the cathode to catalyze the reduction of the electrolyte. One method of depositing platinum is to screen print a thin layer of platinum paste (40) on the cathode (20). An example of the thickness of the layer of platinum paste is about 1 nm though other thickness may be known to a person skilled in the art. The cathode is then sintered at elevated temperatures, and cooled back to room temperature.

Methods of cell assembly are well known to persons skilled in the art. An example of a method by which the solar cell may be assembled is to place a thin gasket material around the dye coated semiconductor material. An example of gasket material is surlyn though other suitable materials would be known to a person skilled in the art. An example of the thickness of the gasket material is about 15 to about 100 μ ^η ι though other thicknesses would be known to a person skilled in the art. The cathode (20) is placed at the top of the area surrounded by the gasket. A current is passed through the cathode (20) to cause resistive heating thereby melting the gasket material and sealing the cell when pressure is applied.

An example of a method by which the solar cell may be filled with electrolyte is to place the cell in a vacuum desiccator with a drop of electrolyte over the hole in the cathode. Vacuum is applied until escaping gases from the cell interior has stopped. The vacuum is released slowly and the electrolyte is drawn into the space between the anode and cathode. The hole in the cathode is sealed either with a strip of bynel and a microscope slide or an aluminum-backed strip of bynel. Other methods of filling the solar cell with electrolyte would be known to a person skilled in the art.

Current collection of the anode (10) and cathode (20) may be enhanced by application of busbars (not shown).

Other means of constructing a DSSC would be well understood by a person skilled in the art.

Operation of a DSSC is well understood by a person skilled in the art and can be understood with reference to Figure 4. The DSSC relies on electron-transfer from a photo-excited dye to a thin mesoporous semi-conductor on an electrode. The dye molecule (55) is subsequently reduced by the electrolyte (45), which, in turn, is regenerated at the cathode (20) by electrons that migrate through an external load (60).

In another aspect of the invention, there is provided a photoelectrochemical cell comprising the compound according to the invention, wherein the compound is used a light absorber to separate water into hydrogen and oxygen.

In another aspect of the invention, there is provided field effect transistor comprising the compound according to the invention, wherein the compound is used as a bistable redox component.

The following examples are presented to enable those skilled in the art to understand and to practice embodiments of the present disclosure. They should not be considered as a limitation on the scope of the present embodiments, but merely as being illustrative and representative thereof.

EXAMPLES

Examples of the invention, including syntheses of particular compounds are provided below. The examples illustrate various aspects of the invention and advantages associated with each. The examples themselves are not to be considered limiting.

EXAMPLE 1

This example describes the synthesis and testing of compounds 1-5, and 7-9, as well as the deprotonated forms of 1 , 3, and 7-9, which are 1a, 3a, and 7a-9a, respectively. The designation and structure of the compounds is shown in Figure 5. Compounds 1 and 1a are baseline dye materials known in the art, and are used herein as a reference point for the comparison of the performance of compounds 2-5, 7-9, 3a, and 7a-9a.

PREPARATION OF EXAMPLE 1 COMPOUNDS

All manipulations were performed using solvents passed through an MBraun solvent purification system prior to use; chloroform (CHCI3) and tetrahydrofuran (THF) solvents were of analytical grade (without stabilizer). All reagents were purchased from Aldrich, except for RuCI ₃ (Pressure Chemical Company), bpy and dcbpyH ₂ (Alfa Aesar). The ligand HL1 (2-phenylpyridine) and phenylboric acid were used as supplied from Aldrich. Purification by column chromatography was carried out using silica (Silicycle: Ultrapure Flash Silica), basic alumina (Fluka), or Sephadex LH-20 (Pharmacia). Analytical thin-layer chromatography (TLC) was performed on

aluminum-backed sheets precoated with silica 60 F254 adsorbent (0.25 mm thick; Merck, Germany) or with plastic-backed sheets precoated with basic alumina 200 F254 adsorbent (0.25 mm thick, Selecto Scientific: Georgia, U.S.A.) and visualized under UV light. ¹ H NMR chemical shifts (δ) are reported in parts per million (ppm) from low to high field and referenced to residual non-deuterated solvent. Standard abbreviations indicating multiplicity are used as follows: s=singlet; d=doublet; t= triplet; m= multiplet.

2-(3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-py ridine

A THF solution containing 2.51 g (10.7 mmol) of 2-(3-bromophenyl)pyridine was cooled to -78 °C. To this solution was added 1 ml. portions of n-BuLi (1.6M in hexanes, 5.1 imL, 13 mmol) resulting in a dark green solution. After 45 min of stirring at -78 °C, 3.0 g (16 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane was added and stirred at -78 °C for 30 min. The dry ice bath was then removed, and the reaction was left to warm to room temperature overnight. The reaction was then quenched with MeOH (5 ml_), preabsorbed on silica, and the solvent was removed in vacuo. The sample was purified using chromatography [Si0 ₂ : (DCM/EtOAc 9:1 ): R _f = 0.57] to afford 2.2 g (73%) of a colorless oil. ¹ H NMR (400 MHz, CDCI ₃ ): δ=8.67 (ddd, ³ J=5 Hz, J=2 Hz, ⁵ J=1 Hz, 1 H, H _a ), 8.37 (s, 1 H, H _e ), 8.11 (ddd, ³ J=8 Hz, J=2 Hz, ⁵ J=1 Hz, 1 H, H _f ), 7.84 (dt, ³ J=8 Hz, ⁴ J=1 Hz, ¹ H, H _h ), 7.77 (dt, ³ J=8 Hz, ⁴ J=1 Hz, 1 H, H _d ), 7.71 (dt, ³ J=7 Hz, ⁴ J=2 Hz, 1 H, H _c ), 7.47 (t, ³ J=8 Hz, H, H _g ), 7.19 (ddd, ³ J=7 Hz, ⁴ J=5 Hz, ⁵ J=1 Hz, 1 H,H _b ), 1.34 (s, 12H, H _Met hyi); ³ C NMR (100 MHz, CDCI ₃ ): δ = 157.7, 149.8, 139.0, 136.8, 135.5, 133.4, 130.0, 128.4, 122.2, 120.9, 84.1 ,

25.1 ;HRMS (El): m/z = 281.1598 [(M) ⁺ ] (calcd for Ci ₇ H ₂ oBN0 ₂ ⁺ : m/z = 281.1587). 2-(2-Nitrophenyl)pyridine (HL2)

An alternative method to a previously reported synthesis is provided. A THF (30 mL) solution containing 500 mg (2.48 mmol) of 1-bromo-2-nitrobenzene was charged with 5.0 mL (2.5 mmol) of a 0.5 THF solution containing 2-pyridylzinc bromide. This mixture was stirred for 5 min prior to the addition of 143 mg (0.124 mmol) of

Pd(PPh ₃ ) ₄ , and then heated at reflux for 15 h. The resultant solution was filtered to obtain a brown filtrate that formed a brown/orange solid upon removal of solvent in vacuo. Purification by column chromatography [Si0 ₂ : (hexanes/EtOAc 5:2)] afforded 265 mg (53.5%) of the product as a yellow oil that solidified upon standing overnight at 4 °C. ¹ H NMR(CDCI ₃ ): δ 8.66 (ddd, ³ J=5 Hz, ⁴ J=1 Hz, ⁵ J=1 Hz, 1 H, H _a ), 7.90 (dd, ³ J=8 Hz, ⁴ J=1 Hz, 1 H, H _h ), 7.80 (td, ³ J=8 Hz, J=2 Hz, 1 H, H _c ), 7.65 (m, 2H, H _e , H _f ), 7.55 (ddd, ³ J=9 Hz, 7 Hz, ⁴ J=2 Hz, 1 H, H _g ), 7.48 (dt, ³ J=8 Hz, ⁴ J=1 Hz, J=1 Hz, 1 H, H _d ), 7.33 (ddd, ³ J = 8 Hz, 5 Hz, J = 1 Hz, 1 H, H _b ). EI-MS: m/z 199.9 (calcd for

CnH ₈ N ₂ 02 ⁺ : m/z 200.0).

2-(3-Nitrophenyl)pyridine (HL3)

An alternative method to a previously reported synthesis is provided. A

THF/EtOH (20 mL) solution (THF:EtOH, 3:1 v:v) containing 501 mg (3.00 mmol) of 3- nitrophenylboronic acid, 966 mg (7.00 mmol) of K ₂ C0 ₃ and 173 mg (0.150 mmol) of Pd(PPh ₃ ) ₄ was charged with 0.26 mL (2.7 mmol) of 2-bromopyridine and then heated at reflux for 65 h. The suspension was then filtered to obtain an orange filtrate that afforded a dark red-orange oil upon removal of solvent in vacuo. Purification by column chromatography [Si0 ₂ : (hexanes/EtOAc/CHCI3 5:2:3)] yields a light yellow solid that was recrystallized from EtOH affording 465 mg (87.2%) of the product as a pale yellow crystalline solid. H NMR(CDCI ₃ ): δ 8.87 (dd, ⁴ J=2 Hz, 2 Hz, ¹ H, H _h ), 8.75 (ddd, ³ J=8 Hz, ⁴ J= 2 Hz, ⁵ J=1 Hz, 1 H, H _a ), 8.38 (ddd, ³ J=8 Hz, ⁴ J=2 Hz, 1 Hz, 1 H, H _g ), 8.28 (ddd, ³ J=8 Hz, ⁴ J=2 Hz, 1 Hz, 1 H, H _e ), 7.83 (m, 2H, H _c , H _d ), 7.66 (dd, ³ J=8 Hz, 8 Hz, 1 H, H _f ), 7.34 (ddd, 1 H, H _b ). EI-MS: m/z 200 (calcd for CiiH ₈ N ₂ 0 ₂ ⁺ : m/z 200.0).

2-(4-Nitrophenyl)pyridine (HL4)

An alternative to a previously reported synthesis is provided A THF (25 mL) solution containing 503 mg (2.49 mmol) of 4-bromo-2-nitrobenzene was charged with 5.0 mL (2.5 mmol) of a 0.5MTHF solution of 2-pyridylzinc bromide and stirred for 5 min prior to the addition of 143 mg (0.124 mmol) of Pd(PPfi ₃ ) . The solution was heated at reflux for 16 h, and then filtered to obtain an orange/brown filtrate. The organic layer was washed with H20 (3 x 15 mL), collected, and the solvent removed in vacuo resulting in a white solid that was purified by column chromatography [Si0 ₂ : (hexanes/EtOAc/CHCIa 5:2:3)] to afford 276 mg (55.4%) of the product as a white solid. ¹ H NMR(CDCI ₃ ): δ 8.76 (dt, ³ J=5 Hz, ⁴ J=1 Hz, ⁵ J=1 Hz, 1 H, H _a ), 8.34 (dt, ³ J=9 Hz, ⁴ J=2 Hz, ⁵ J=2 Hz, 2H, H _f ), 8.19 (dt, ³ J=9 Hz, ⁴ J=2 Hz, ⁵ J=2 Hz, 2H, H _e ), 7.87-7.82 (m, 2H, He, Ha), 7.35 (ddd, ³ J=7 Hz, 5 Hz, ⁴ J = 2 Hz, 1 H, H _b ). EI-MS: m/z 199.9 (calcd for CnH8N ₂ 0 ₂ ⁺ : m/z 200.0).

2-(2,4-Dinitrophenyl)pyridine (HL5)

A THF (25 mL) solution containing 1 .012 mg (4.097 mmol) of 1-bromo-2,4- dinitrobenzene was charged with 8.3 mL (4.2 mmol) of a 0.5 THF solution containing 2-pyridylzinc bromide and stirred for 5 min prior to the addition of 240 mg (0.208 mmol) of Pd(PPh ₃ )4- The solution was heated at reflux for 17 h, and then filtered to obtain a brown filtrate. Subsequent solvent removal in vacuo left a dark orange/brown oil that was purified by column chromatography [Si0 ₂ :

(hexanes/EtOAc/CHCI ₃ 5:2:3)] to afford 604 mg (60.2%) of the product as a yellow oil that solidified upon standing overnight at 4 °C. ¹ H NMR (CDCI ₃ ): δ 8.74 (d, ⁴ J=2 Hz, 1 H, H _g ), 8.70 (ddd, ³ J=5 Hz, ⁴ J=1 Hz, ⁵ J=1 Hz, 1 H, H _a ), 8.51 (dd, ³ J = 8 Hz, ⁴ J = 2 Hz, 1 H, H _f ), 7.87 (m, 2H, H _c , H _e ), 7.55 (dt, ³ J=8 Hz, ⁴ J=1 Hz, ⁵ J=1 Hz, 1 H, H _d ), 7.41 (ddd, ³ J=8Hz, 5 Hz, J=1 Hz, 1 H, H _b ). ¹³ C NMR (CDCI ₃ ): 153.4, 150.4, 149.5, 147.7, 140.8, 137.4, 132.7, 126.8, 124.2, 123.0, 120.2. HRMS (El): m/z 245.0444 [(M ⁺ )] (calcd for d 1 H ₇ N ₃ 0 ₄ ⁺ : m/z 245.0437).

2-(Biphenyl-3-yl)pyridine) (HL7)

A sparged mixture of THF (45 mL) and H ₂ 0 (5 mL) containing 0.69 g (3.0 mmol) of 2-(3-bromophenyl)pyridine38 and 400 mg (3.28 mmol) of phenylboronic acid was charged with 2.27 g (16.4 mmol) of K ₂ C0 ₃ and 265 mg (0.229 mmol) of

Pd(PPh ₃ ) ₄ . The suspension was heated at reflux for 14 h under an inert atmosphere, then cooled and poured into H ₂ 0. The product was extracted with diethyl ether, washed with brine, and then dried with MgS0 ₄ . Filtration and removal of the solvent in vacuo resulted in an oil that was purified by column chromatography [basic Al ₂ 0 ₃ : DCM/hexane1 :1 ; R _f =0.78] affording 650 mg (95.2%) of the product as a colorless oil. ¹ H NMR (400 MHz, CDCI ₃ ): δ=8.78 (ddd, ³ J= 5 Hz, ⁴ J=2 Hz, ⁵ J=1 Hz, 1H,H _a ), 8.32 (t, ⁴ J=2 Hz, ¹ H, He), 8.03 (dt, ³ J = 8 Hz, ⁴ J = 2 Hz, ⁵ J = 1 Hz, ¹ H, H _f ), 7.85-7.67 (m, ⁵ H, Hd, H _h , He, Hi), 7.59 (t, ³ J=8 Hz, 1 H, H _g ), 7.51 (t, ³ J= 7 Hz, 2H,H _j ), 7.42 (t, ³ J=7 Hz, 1H, H _k ), 7.28 (ddd, ³ J=7 Hz, ⁴ J = 5 Hz, ⁵ J = 1 Hz, 1 H, Hb); ¹³ C NMR (100 MHz, CDCI ₃ ): δ =157.1 , 149.4, 141.7, 140.9, 139.6, 136.9, 129.2, 128.8, 127.8, 127.4, 127.2, 125.8, 122.2, 120.6; HRMS (El): m/z = 231.1042 [(M) ⁺ ] (calcd for C ₁₇ H ₁₃ N ⁺ : m/z = 231.1048).

2,4'-(1 ,3-phenylene)dipyridine (HL8)

A sparged mixture of THF(45 ml_) and H ₂ 0(5 mL) containing 330 mg( .17 mmol) of 2-(3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)pyridine (Lo et al. Macromolecules. 2003, 36, 9721-9730) and 251 mg (1.29 mmol) of 4-bromopyridine was charged with 81 mg (5.88 mmol) of K ₂ C0 ₃ and 95 mg (0.082 mmol) of

Pd(PPh ₃ ) ₄ . The suspension was heated at reflux for 14 h under inert atmosphere. The reaction mixture was then cooled and poured into H ₂ 0. The product was extracted with diethyl ether, washed with brine, and then dried with MgS0 ₄ . Filtration and removal of the solvent in vacuo resulted in an oil thatwas purified using column chromatography [Si0 ₂ : using a gradient DCM/EtOAc 8:2 to remove impurities and then increasing to the more polar DCM/EtOAc/MeOH 8:1 :1] to afford 200 mg (73%) of the product as a colorless oil. ¹ H NMR (400MHz, CDCI3): δ=8.63 (d, ³ J=5Hz, 1 H, Ha), 8.58 (d, ³ J=6 Hz, 2H, Η,), 8.23 (s, 1 H, He), 7.94 (d, ³ J=8 Hz, 1 H,H _f ), 7.70-7.64 (m, 2H,H _dl H _c ), 7.57 (d, ³ J = 8 Hz, 1 H, H _h ), 7.50-7.45 (m, 3H, Hj, H _g ), 7.16 (ddd, ³ J=7 Hz, ⁴ J=5Hz, ⁵ J=1 Hz, 1 H, H _b ). ¹³ CN R(100 Hz, CDCI ₃ ): 5=156.5, 150.1 , 149.6, 148.1 ,

140.1 , 138.4, 136.8, 129.4, 127.4, 127.3, 125.5, 122.4, 121.6, 120.5. HRMS (El): m/z = 232.1007 [(M) ⁺ ] (calcd for Ci ₆ Hi ₂ N ₂ ⁺ : m/z = 32.1000).

5-(3-(Pyridin-2-yl)phenyl)thiophene-2-carbaldehyde (HL9)

A sparged mixture of THF (45 mL) and H ₂ 0 (5 mL) containing 1.10 g (3.91 mmol) of 2-(3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)pyridine (Lo et al. Macromolecules. 2003, 36, 9721-9730) and 747 mg (3.91 mmol) of 5- bromothiophene-2-carbaldehyde was charged with 2.70 g (19.6 mmol) of K2CO3 and 316 mg (0.273 mmol) of Pd(PPh ₃ ) ₄ . The mixture was heated at reflux for 14 h under inert atmosphere, then cooled and poured into H ₂ 0. The product was extracted with diethyl ether, washed with brine and dried with MgS0 ₄ . Filtration and removal of the solvent in vacuo resulted in an oil that was purified by column chromatography [Si0 ₂ : (DCM/EtOAc 9:1 ): R _f =0.57] to afford 820 mg (79.0%) of the product, an oil that solidified as a yellow solid upon standing. ¹ H NMR (400 MHz, CDCI ₃ ): 5=9.87 (s, 1 H, Hk), 8.70 (ddd, ³ J=5 Hz, ⁴ J=2 Hz, ⁵ J=1 Hz, 1 H, H _a ), 8.31 (t, ⁴ J=2 Hz, 1 H, He), 7.95 (ddd, ³ J=8 Hz, ⁴ J=2 Hz, ⁵ J=1 Hz, 1 H, H _f ), 7.83-7.75 (m, 3H,H _c ,H ,H _j ), 7.67 (dt, ³ J=8 Hz, ⁴ J=1 Hz, 1 H, H _d ), 7.50 (t, ³ J=8 Hz, 1H, H _g ), 7.47 (d, ³ J=8 Hz, 1 H, Η,), 7.25 (ddd, ³ J=7 Hz, ⁴ J = 5 Hz, ⁵ J = 1 Hz, 1 H, H _b ); 13C NMR (100 MHz, CDCI ₃ ): 5 = 183.0, 156.6,

154.2, 150.0, 142.8, 140.6, 137.5, 137.1 , 133.8, 129.8, 128.0, 127.0, 125.2, 124.7, 122.8, 120.8; HRMS (El): m/z = 265.0548 [(M) ⁺ ] (calcd for Ci ₆ HnNOS ⁺ :m/z =

265.0561 ).

General Synthetic Procedure for Precursors P1-P5, P7-P9

The addition of HL1-HL5, HL7-HL9 to the Ru precursor, [(n, ⁶ -p-cymene)RuCI ₂ ] ₂ , leads to a mixture of [Ru(CH ₃ CN) ₄ (L#)]PF ₆ and [Ru(pcymene)(CH ₃ CN) ₂ (L#)]PF6

(denoted P#; Figure 1 ). While it is possible to isolate each of these cyclometalated Ru species, they both serve as satisfactory precursors to the target metal complexes. General synthetic protocol: A flask containing 0.33 mmol of [(n ⁶ -p-cymene)RuCI ₂ ]2, 0.66 mmol of HL#, 0.66 mmol of NaOH and 1.32 mmol of KPF ₆ in 5 ml. of MeCN was stirred at 45 °C for 2 days (Figure 1). The resultant reaction mixture was filtered to remove the suspended solid. The solvent was then removed in vacuo, and

reconstituted in a minimum volume of a 9:1 CH ₂ CI ₂ /MeCN solvent mixture and purifiedby column chromatography [basic ΑΙ ₂ 0 ₃ : (CH ₂ CI ₂ /MeCN 9:1)]. The

yellow/orange band was collected, and the solvent was removed. The crude product was precipitated using CH ₂ CI ₂ / diethyl ether, filtered, and washed with diethyl ether to afford the desired mixture P#. The mixture was verified by ¹ H NMR spectroscopy, and used as prepared in subsequent reactions without further separation or purification.

[Ru(p-cymene)(CH ₃ CN) ₂ (L1)]PF ₆ (P1)

An MeCN (5 mL) suspension containing 101 mg (0.653 mmol) of HL1, 26 mg (0.65 mmol) of crushed NaOH, 241 mg (1.31 mmol) of KPF ₆ and 199 mg (0.325 mmol) of [(o ⁶ -p-cymene)RuCI ₂ ] ₂ was stirred at 45 °C for 2 days. The reaction mixture was then cooled and filtered to remove suspended solid, followed by the removal of solvent in vacuo to yield an orange/brown solid. The solid was purified by column chromatography [basic Al ₂ 0 ₃ : (CH ₂ CI ₂ / MeCN 9:1 )]. The yellow fraction that was collected and reconstituted in a minimum volume of CH ₂ CI ₂ , and was then drawn out of solution with diethyl ether. The resultant solid was filtered, washed with diethyl ether (3 x 10 mL), and dried to afford 280 mg (69.9%) of the product as a yellow/green solid. ¹ H NMR(CD ₃ CN): δ 9.20 (td, ³ J=6 Hz, ⁴ J=1 Hz, 1H), 8.14 (dd, ³ J = 8 Hz, ⁴ J = 1 Hz, 1 H), 7.91 (m, 2H), 7.76 (dd, ³ J = 8 Hz, ⁴ J=1 Hz, 1 H), 7.25 (m, 2H), 7.15 (dt, ³ J=8 Hz, J=1 Hz, 1 H) 5.93 (d, ³ J=6 Hz, 2H), 5.65 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1H), 5.41 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 2.35 (septet, ³ J=7 Hz, 1 H), 2.12 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H), 0.93 (d, ³ J=7 Hz, 3H), 0.91 (d, ³ J=7 Hz, 3H). ¹³ C NMR(CD ₃ CN): 176.0, 166.6, 156.8, 145.5, 141.1 , 139.7, 130.7, 125.4, 124.8, 123.7, 120.5, 105.0, 103.3, 93.4, 89.3, 85.7, 31.9, 22.5, 22.3, 18.9, 3.9.

[Ru(CH ₃ CN) ₄ (L5)lPF ₆ (P5)

A MeCN (5 mL) suspension containing 161 mg (0.657 mmol) of HL5, 26 mg (0.65 mmol) of crushed NaOH, 241 mg ( .30 mmol) of KPF ₆ and 200 mg

(0.327 mmol) of [(i-| ⁶ -p-cymene)RuCI ₂ ]2 was refluxed for 2 days and then filtered to yield a deep purple solution. Solvent was removed in vacuo, and the resultant solid was reconstituted in a minimum volume of 9:1CH ₂ CI ₂ /MeCN and purified by column chromatography [basic Al ₂ 0 ₃ : (CH ₂ CI ₂ /MeCN 9:1 )]. After the solvent was removed in vacuo, the residual solid was dissolved in a minimal volume of MeCN and drawn out of solution by the slow addition of diethyl ether. The solid was isolated and washed with diethyl ether (3 * 10 mL) to afford 144 mg (34.2%) of a pink solid product. ¹ H NMR (CD ₃ CN): δ 9.13 (ddd, ³ J=6 Hz, ⁴ J=2 Hz, ⁵ J=1 Hz, 1 H), 8.90 (d, ⁴ J=2 Hz, 1 H), 7.92 (d, ⁴ J=2 Hz, 1 H), 7.83 (ddd, ³ J=9 Hz, 8 Hz, ⁴ J=2 Hz, 1 H), 7.52 (dt, ³ J=8 Hz, J=1 Hz, 1 H), 7.38 (ddd, ³ J=7 Hz, 6 Hz, ⁴ J=1 Hz, 1 H), 2.57 (s, 3H), 2.02 (s, 6H), 1 .97 (s, 3H). ³ C NMR (CD ₃ CN): 197.2, 162.4, 155.0, 148.6, 145.8, 142.4, 138.1 , 134.2, 125.3, 125.2, 123.1 , 123.0, 112.2, 4.5, 4.0.

General Synthetic Procedure for 1-4

A degassed aqueous MeOH solution (5 mL; H20/MeOH, 1 :4 v.v) containing 0.20 mmol of dcbpyH ₂ and 0.40 mmol of crushed NaOH was stirred for 40 min prior to the addition of 0.10 mmol of P#. The solution was brought to reflux for 3 h, cooled to room temperature, followed by the removal of solvent in vacuo. The resultant dark purple solid was reconstituted in H ₂ 0, followed by the dropwise addition of 0.2M HPF ₆ until the formation of a precipitate was observed. The isolated precipitate was washed withH ₂ 0 (3 x 10 mL), reconstituted in DMF, and then drawn out of solution with diethyl ether. The solid was collected by filtration, washed with diethyl ether (3 x 10 mL), and dried in air.

[Ru(dcbpyH ₂ ) ₂ (L1)lPF ₆ (1)

Yield: 55 mg (61%) of the product as a dark purple solid. Characterization data matches the previously reported synthesis.

[Ru(dcbpyH ₂ ) ₂ (L2)]PF6 (2)

Yield: 93 mg (77%) of the product as a dark purple solid. ¹ H NMR (CD ₃ OD with a drop of NaOD): δ 9.11 (s, 1 H), 9.04 (s, 1 H), 8.98 (s, 2H), 8.22 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.94 (m, 4H), 7.75 (m, 5H), 7.58 (d, ³ J=8 Hz, 1 H), 7.07 (m. 2H), 6.95 (t, ³ J=8 Hz, 1 H), 6.61 (dd, ³ J=8 Hz, ⁴ J = 1 Hz, 1H). ESI-MS: m/z 789.02 (calcd for RuCas^aNeO 789.05). Anal. Calcd. for RuCss^sNeOioPFe: C, 45.03; H, 2.48; N, 9.00. Found: C, 45.43, H, 2.77, N, 9.37.

[Ru(dcbpyH ₂ ) ₂ (L3)]PF ₆ <3)

Yield: 178 mg (87.4%) of the product as a dark purple solid. ¹ H N R (CD ₃ OD): δ 9.04 (s, 1 H), 8.96 (s, 1 H), 8.92 (s, 1 H), 8.90 (s, 1 H), 8.68 (d, ⁴ J = 2 Hz, 1H), 8.27 (d, ³ J=8 Hz, 1 H), 7.99 (d, ³ J=6 Hz, 1 H), 7.92-7.88 (m, 2H), 7.85-7.75 (m, 3H), 7.70 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.68-7.56 (m, 3H), 7.50 (d, ³ J = 6 Hz, 1 H), 7.10 (ddd, ³ J = 7 Hz, 6 Hz, ⁴ J = 1 Hz 1 H), 6.74 (d, ³ J = 8 Hz, 1 H). HRMS (MALDI-TOF): m/z 789.0492 [M ⁺ ] (calcd for C ₃ 5H23N ₆ O ₁₀ Ru ⁺ : m/z 789.0523). Anal. Calcd. for RuC ₃ 5H23N6O ₀ PF6 ⁺ 7H ₂ 0: C, 39.67; H, 3.52; N, 7.93. Found: C, 39.74; H, 3.19; N, 7.92.

[Ru(dcbpyH ₂ ) ₂ (L4)]PF ₆ (4)

Yield: 32 mg (99.0%) of the product as a dark purple solid. ¹ H NMR (CD ₃ OD with a drop of NaOD): δ 9.03 (s, 1 H), 8.96 (s, 1 H), 8.95 (s, 1 H), 8.90 (s, 1 H), 8.26 (d, ³ J=8 Hz, 1 H), 8.08 (d, ³ J=9 Hz, 1 H), 8.03 (d, ³ J=6 Hz, 1 H), 7.76 (m, 10H), 7.23 (d, J=2 Hz, 1 H), 7.13 (dd, ³ J=8 Hz, ⁴ J=1 Hz, 1 H). ¹³ C NMR (CD ₃ OD with a drop of NaOD): 195.8, 171.2, 171.1 , 171.0, 170.9, 170.7, 166.8, 159.3, 158.5, 158.3, 157.0, 155.4, 153.8, 151.9, 151.3, 151.2, 150.3, 148.7, 147.9, 146.6, 145.7, 145.6, 137.7, 129.6, 127.8, 127.4, 126.9, 126.8, 125.5, 124.2, 124.1 , 24.0, 123.8, 122.2, 117.5. HRMS(ESI): m/z = 789.05200 [M ⁺ ] (calcd for RuC35H ₂₃ N ₆ Oio] ⁺ : m/z = 783.05196). Anal. Calcd. for RuC3 ₅ H ₂₃ N ₆ OioPFe ⁺ DMF + 2H ₂ 0: C, 50.84; H, 3.82; N, 10.92. Found: C, 50.63; H.3.91 ; N, 10.83.

[Ru(dcbpyH ₂ ) ₂ (L5)]PF ₆ (5)

A degassed aqueous methanol solution (5 ml_; H ₂ 0/MeOH, 1 :4 v:v) containing 22 mg (0.092 mmol) of dcbpyH ₂ and 7 mg (0.2 mmol) of crushed NaOH was stirred for 40 min prior to the addition of 30 mg (0.046 mmol) of P5. The light purple solution was brought to reflux for 3 h and then cooled to room temperature. Removal of solvent in vacuo yielded a dark purple solid that was purified by column chromatography [Si0 ₂ : (12 cm x 2 cm)(MeOH/CHCI ₃ 3:1 )]. The purple band was collected followed by the removal of solvent in vacuo. The resultant solid was dissolved in a minimum volume of MeOH and drawn out of solution with acetone. The solid was collected by filtration and washed with diethyl ether (3 x 10 mL). The solid was reconstituted inH ₂ 0, followed by the dropwise addition of 0.2 M HPF ₆ until the formation of a precipitate was observed. The solid was collected by filtration, washed with H ₂ 0 (3 x 10 ml_), and then reconstituted in DMF and drawn out of solution with diethyl ether. The solid was isolated, washed with diethyl ether (3 x 10 ml_), and dried to afford 25 mg (56%) of the product as a dark purple solid. H NMR (CD ₃ OD with a drop of NaOD): δ 9.05 (s, 1 H), 8.98 (s, 2H), 8.94 (s, 1 H), 8.02 (d, ³ J=6 Hz, 1 H), 7.75 (m, 11 H), 7.47 (d, ⁴ J=2 Hz, 1 H), 7.19 (ddd, ³ J=7 Hz, 6 Hz, J=1 Hz, 1 H). ¹³ C NMR (D ₂ 0 with a drop of NaOD and MeOD): 202.5, 172.7, 172.6, 172.4, 172.2, 169.5, 161.1 , 158.8, 157.9, 157.8, 156.3, 155.6, 152.8, 151.9, 151.6, 150.5, 148.5, 45.8, 145.6, 144.6, 144.1 , 144.0, 142.2, 137.3, 132.1 , 127.0, 126.9, 126.5, 126.4, 126.2, 124.3, 123.7, 123.6, 123.5, 112.5. ESI-MS: m/z 833.95 [M ⁺ ] (calcd for RuC ₃ 5H22N ₇ 0 ₁₂ 834.04). Anal. Calcd. For

RuCssHssNeO^PFe + 2CH ₃ OH: C, 42.62; H, 2.90; N, 9.40. Found: C, 43.02; H,3.18; N, 9.66.

[Ru(dcbpyH ₂ )(dcbpyH)(L7)] (7)

A degassed aqueous methanol (15 ml_) solution (H ₂ 0/MeOH, 1 :4 v.v) containing 194 mg (0.794 mmol) of dcbpyH ₂ and 64 mg (1.6 mmol) of crushed NaOH was stirred for 40 min prior to the addition of 261 mg (0.401 mmol) of P8. The reaction mixture was brought to reflux for 3 h generating a color change from yellow/green to dark purple. Insoluble particulates were removed from the solution by filtration, followed by the removal of solvent from the filtrate in vacuo. Further purification by column chromatography [Si0 ₂ : (MeOH/CHCI ₃ 3: 1 ) followed by Sephadex LH- 20:

(D ₂ 0)] yielded the deprotonated product as a sodium salt. The solid was reconstituted in H ₂ 0, followed by the addition of 0.2 M HN0 ₃ until the formation of a precipitate was observed and placed in the refrigerator overnight. The solid was isolated by filtration, washed with acid (pH 3) and dried in vacuo to afford 51 mg (14%) of the dark purple product. 1 H NMR (CD ₃ OD with a drop of NaOD): δ 9.03 (s, 1 H), 8.95 (s, 1 H), 8.91 (s, 1 H), 8.88 (s, 1 H), 8.22 (dd, ³ J = 6 Hz, ⁴ J = 2 Hz, 1 H), 8.19 (d, ³ J=8 Hz, 1 H), 8.11 (d, ³ J=2 Hz, H), 7.94 (dd, ³ J=6 Hz, ⁴ J = 1 Hz, 1 H), 7.87 (dd, ³ J = 6 Hz, ⁴ J = 1 Hz, 1 H), 7.86 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.83 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.73 (ddd, ³ J=9 Hz, 7 Hz, J=2 Hz, 1 H), 7.68 (dd, ³ J=6 Hz, ⁴ J = 2 Hz, 1H), 7.65-7.60 (m, 4H), 7.56 (ddd, ³ J = 6 Hz, J=2 Hz, ⁵ J=1 Hz, 1 H), 7.37 (t, ³ J=7 Hz, 2H), 7.23 (t, ³ J=7 Hz, 1 H), 7.12 (dd, ³ J=8 Hz, ⁴ J=2 Hz, 1 H), 6.98 (ddd, ³ J=7 Hz, 6 Hz, ⁴ J=1 Hz, 1 H), 6.51 (d, ³ J=8 Hz, 1H). Anal. Calcd. for RuC ₄₁ H ₂ 7N ₅ 08 + 2H ₂ 0: C, 57.61 ; H, 3.66; N, 8.19. Found: C, 57.29; H, 3.72; N, 8.04. [Ru(dcbpyH) ₂ (L8-H)] (8)

A degassed H ₂ 0/MeOH (15 mL) solution (H ₂ 0/MeOH, 1 :4 v:v) containing 218 mg (0.892 mmol) of dcbpyH ₂ and 72 mg ( .8 mmol) of crushed NaOH was stirred for 40 min prior to the addition of 287 mg (0.440 mmol) of P9. The solution was brought to reflux for 3 h leading to a color change from yellow to dark purple. A reaction workup analogous to that of 7 affords 26 mg (6%) of a dark purple product. ¹ H NMR (CD ₃ OD with a drop of NaOD): δ 9.04 (s, 1 H), 8.95 (s, 1 H), 8.91 (s, 1 H), 8.89 (s, 1 H), 8.49 (dd, ³ J=5 Hz, ⁴ J=2 Hz, 2H), 8.28 (m, 2H), 8.17 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.93 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1H), 7.87 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1H), 7.85 (dd, ³ J=6 Hz, J=1 Hz, 1 H), 7.82 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.78 (ddd, ³ J=9 Hz, 8 Hz, ⁴ J=2 Hz, 1 H), 7.75 (dd, ³ J=5 Hz, J=2 Hz, 2H), 7.69 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.66 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.61 (m, 2H), 7.24 (dd, ³ J= 8 Hz, ⁴ J = 2 Hz, 1 H), 7.03 (ddd, ³ J = 7 Hz, 6 Hz, ⁴ J = 1 Hz, 1 H), 6.63 (d, ³ J=8 Hz, 1 H). ¹³ CNMR (CD ₃ OD with a drop of NaOD): 198.9, 171.4, 171.3, 171.1 , 171.0, 168.4, 159.4, 158.7, 158.3, 156.9, 155.3, 151.8, 151.4, 151 .2, 151.0, 150.4, 150.1 , 148.0, 147.7, 146.4, 145.3, 145.1 , 137.5, 137.4, 131.5, 127.8, 127.6, 127.1 , 126.7, 126.6, 124.1 , 124.0, 123.7, 123.6, 123.0, 122.4, 120.7. HRMS ( ALDI-TOF): m/z = 821 .0962 [M ⁺ ] (calcd for [RuC ₄ oH28 ₆ 0 ₈ ]

+:m/z=821.0939). Anal. Calcd. For RuC^e eOe + 3H ₂ 0: C, 53.87; H, 3.84; N, 9.43. Found: C, 53.61 ; H, 3.26; N, 9.42.

[Ru(dcbpyH ₂ )(dcbpyH)(L9)] (9)

A degassed methanol (250mL) solution charged with 75 mg (0.11 mmol) of P9, 53 mg (0.22 mmol) of dcbpyH ₂ and 18 mg (0.44 mmol) of crushed NaOH was heated at reflux for 3 h. The solvent was then removed in vacuo, and the resultant solid was purified by column chromatography [Si0 ₂ : (MeOH/KN0 ₃ (aq, sat)/1% acetic acid 5:1 :1 )]. The isolated solid was reconstituted in H ₂ 0 and acidified with 0.2 M HNO3 until the formation of a precipitate was observed. The solid was isolated, washed with H ₂ 0 and diethyl ether, and dried in vacuo to afford 65 mg (70%) of the product as a purple/red solid. 1H NMR (CD ₃ OD with a drop of NaOD): δ 9.77 (s, 1 H), 9.03 (s, 1 H), 8.95 (d, J=1 Hz, 1 H), 8.91 (d, ⁴ J =1 Hz, 1 H), 8.89 (d, J= 1 Hz, 1 H), 8.22 (m, 2H), 8.15 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.92 (dd, ³ J=6 Hz, J=1 Hz, 1 H), 7.88-7.75 (m, ³ J=6 Hz, ⁴ J=1 Hz, 5H), 7.69 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.66 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.62 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.60 (ddd, ³ J=7 Hz, J = 2 Hz, ⁵ J = 1 Hz, 1 H), 7.55(d, ³ J = 4 Hz, 1 H), 7.19 (dd, ³ J=8 Hz, ⁴ J=2 Hz, 1 H), 7.03 (ddd, ³ J=7 Hz, 6 Hz, ⁴ J=1 Hz, 1 H), 6.58 (d, ³ J= 8 Hz, 1 H). HRMS (MALDI-TOF): m/z 854.0488 [M ⁺ ] (calcd for C ₄ oH26 ₅ 0 ₉ SRu ⁺ : m/z 854.0500). Anal. Calcd. for + 3H ₂ 0: C, 52.98; H, 3.45; N, 7.72. Found: C, 53.05; H, 3.21 ; N, 7.70.

General Synthetic Procedure for 1a, 7a-9a

An aqueous (20 mL) suspension containing 0.1 12 mmol of 1 was titrated with 0.2M tetrabutylammonium hydroxide (NBu ₄ OH) to reach pH 7. Solid impurities were removed by filtration, followed by the removal of solvent in vacuo. The resultant solid was reconstituted in MeOH and then drawn out of solution using a 1 :1 mixture of diethyl ether/petroleum ether and purified by column chromatography [Sephadex LH- 20: (H ₂ 0)]. Solvent was removed from the dark purple fraction in vacuo leaving a solid that was dried overnight under reduced pressure to afford the product.

(Bu ₄ N) ₃ [Ru(dcbpy)(dcbpyH)(L1)]PF ₆ (1a)

Yield: 73 mg (40%) of the product as a dark purple solid. ¹ H NMR(CD ₃ OD):6 9.01 (s, 1H), 8.94 (s, 1 H), 8.89 (s, 1H), 8.87 (s, 1H), 8.14 (dd, ³ J = 6Hz, ⁴ J=1 Hz, 1H), 8.06 (d, ³ J=8 Hz, 1 H), 7.91 (d, ³ J=6Hz, ⁴ J= 1 Hz, 1 H), 7.88-7.84 (m, 3H), 7.79 (dd, ³ J=6Hz, J=1 Hz, 1 H), 7.71 (ddd, ³ J=9 Hz, 8 Hz, ⁴ J=2 Hz, 1 H), 7.67 (dd, ³ J=6Hz, ⁴ J=2 Hz, 1 H), 7.64 (dd, ³ J=6Hz, J=2 Hz, H), 7.60 (dd, ³ J=6Hz, ⁴ J=2 Hz, 1H), 7.55 (ddd, ³ J=6Hz, ⁴ J=2Hz, ⁵ J=1 Hz,1 H), 6.96 (ddd, ³ J=7 Hz, 6 Hz, J=1 Hz, 1 H), 6.90 (ddd, ³ J=7Hz, 7Hz, J=1 Hz, 1H), 6.81 (ddd, ³ J=7 Hz, 7 Hz, ⁴ J=1 Hz, 1 H), 6.40 (dd, ³ J=7Hz, ⁴ J=1 Hz, 1 H), 3.22 (m, 24H), 1.64 (m, 24H), 1.38 (sextet, ³ J=7 Hz, 24H), 0.98 (t, ³ J=7 Hz, 36H). ESIMS: m/z = 744.2 [(M - 3Bu ₄ N ⁺ + 4H ⁺ ) ⁺ ] calcd for RuC ₃₅ H2 N ₅ C : m/z = 744.1 ). Anal. Calcd. for 4H ₂ 0: C, 59.16; H, 7.91 ; N, 6.81. Found: C, 59.42; H, 8.19; N, 6.65.

(Bu ₄ N) ₄ [Ru(dcbpy) ₂ (L3)]PF ₆ (3a)

A suspension containing 100 mg (0.107 mmol) of 1 in 20 mL of Η ₂ 0 was titrated with 0.2 M NBu ₄ OH to reach pH 7 and then filtered. Removal of solvent in vacuo yielded an oily solid that was reconstituted in MeOH and brought out of solution with a 1 :1 mixture of diethyl ether/petroleum ether. The isolated solid was dried overnight under vacuum to afford 94 mg (46%) of a dark purple solid product. ¹ H NMR(CD ₃ OD): δ 9.05 (s, 1H), 8.96 (s, 1 H), 8.93 (s, 1H), 8.90 (s, 1 H), 8.68 (d, ⁴ J = 2 Hz, 1 H), 8.26 (d, ³ J = 8 Hz,1 H), 7.99 (d, ³ J=6 Hz, 1 H), 7.92-7.88 (m, 2H), 7.84-7.76 (m, 3H), 7.71 (dd, ³ J = 6 Hz, ⁴ J = 2 Hz, 1 H), 7.68-7.60 (m, 3H), 7.56 (d, ³ J=6 Hz, 1H), 7.10 (ddd, ³ J=7 Hz, 6 Hz, ⁴ J=1Hz 1 H), 6.75 (d, ³ J=8 Hz, 1H), 3.23 (m, 32H), 1.65 (m, 32H), 1.40 (sextet, ³ J=7 Hz, 32H), 1.00 (t, ³ J=7Hz, 48H). ESI-MS:m/z=789.1 [(M - 3Bu ₄ N ⁺ + 4H ⁺ ) ⁺ ] (calcd for RuCssHas eO^: m/z=789.1 ). Anal. Calcd. for

RuC ₉₉ Hi ₇ i ioOi ₄ PF ₆ + 4H ₂ 0: C, 60.31 ; H, 8.74; N, 7.10. Found: C, 60.40; H, 8.47; N, 7.39.

(Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L7)] (7a)

Yield: 48 mg (62%) of the product as a dark purple solid. ¹ H NMR (CD ₃ OD): δ

9.03 (s,1 H), 8.95 (s, 1 H), 8.91 (s, 1 H), 8.89 (s, 1 H), 8.22 (m, 2H), 8.13 (d, ⁴ J = 2 Hz, 1H), 7.94 (d, ³ J = 6 Hz, 1 H), 7.87 (m, 2H), 7.83 (d, ³ J=6 Hz, 1 H), 7.74 (ddd, ³ J=8 Hz, 7 Hz, J=2 Hz, 1 H), 7.68 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.66-7.61 (m, 4H), 7.57 (d, ³ J=6 Hz, 1 H), 7.38 (t, ³ J=7 Hz, 2H), 7.24 (t, ³ J=7 Hz, 1 H), 7.12 (dd, ³ J=8 Hz, ⁴ J=2 Hz, 1 H), 6.99 (ddd, ³ J=7 Hz, 6 Hz, ⁴ J=1 Hz, 1 H), 6.53 (d, ³ J=8 Hz, 1 H), 3.20 (m, 24H), 1.62 (m, 24H), 1.37 (sextet, ³ J=7 Hz, 24H), 0.97 (t, ³ J=7 Hz, 36H). ¹³ C NMR (CD ₃ OD): 193.3, 171.3, 171.1 , 171.0, 168.8, 159.4, 158.7, 158.3, 157.0, 155.4, 151.3, 151.1 , 151 .0, 150.2, 147.9, 147.4, 146.4, 145.3, 145.0, 143.5, 137.3, 136.9, 135.6, 129.9, 128.5, 127.8, 127.6, 127.4, 127.0, 126.6, 124.0, 123.9, 123.8, 123.7, 123.6, 123.5, 120.4, 59.7, 24.9, 20.8, 14.1. ESI-MS: m/z = 820.1 [(M - 3Bu ₄ N ⁺ + 4H ⁺ ) ⁺ ] (calcd for

RuC ₄ i H2 _{8 5} 08 ⁺ : m/z = 820.1 ). Anal. Calcd. for RuCegHusNeOie + 8H ₂ 0: C, 63.36; H, 8.84; N, 6.64. Found: C, 63.57; H, 8.64; N, 6.59.

(Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L8)] (8a)

Yield: 36 mg (84%) of the product as a dark purple solid. ¹ H NMR (CD ₃ OD): δ 9.05 (s, 1 H), 8.96 (d, ⁴ J = 1 Hz, 1 H), 8.92 (d, ⁴ J = 1 Hz, 1 H), 8.89 (d, ⁴ J=1 Hz, 1 H), 8.49 (d, ³ J=6 Hz, 2H), 8.28 (m, 2H), 8.17 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.94 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.89-7.82 (m, 3H), 7.80-7.75 (m, 3H), 7.70 (dd, ³ J = 6 Hz, ⁴ J = 2 Hz, 1 H), 7.66 (dd, ³ J = 6 Hz, ⁴ J = 2 Hz, 1 H), 7.61 (m, 2H), 7.25 (dd, ³ J=8 Hz, J=2 Hz, 1H), 7.03 (ddd, ³ J=7 Hz, 6Hz, J=1 Hz, 1 H), 6.63 (d, ³ J=8 Hz, 1 H), 3.22 (m, 24H), 1.63 (m, 24H), 1.38 (sextet, ³ J=7 Hz, 24H), 0.98 (t, ³ J=7 Hz, 36H). ¹³ C NMR (CD30D): 199.1 , 171.1 , 170.9, 170.8, 168.4, 159.3, 158.7, 158.3, 156.9, 155.3, 151.8, 151.4, 151.1 ,

151.0, 150.4, 150.2, 148.1 , 146.6, 145.5, 37.5, 131.4, 127.8, 127.6, 127.1 , 126.7,

124.1 , 124.0, 123.8, 123.7, 123.0, 122.4, 120.7, 59.6, 24.9, 20.8, 14.1. ESI-MS:

m/z=821.2 [(M - 3Bu N ⁺ + 4Η*) ⁺ ] (calcd for m/z = 821.1 ). Anal. Calcd. For RuC ₈₈ H ₁₄ 7N ₉ Oi6 + 8H ₂ 0: C, 62.61 ; H, 8.78; N, 7.47. Found: C, 62.43; H, 8.72; N, 7.26.

(Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L9)] (9a)

Yield: 45 mg (59%) of the product as a dark purple solid. H NMR (CD ₃ OD): δ 9.80 (s, H), 9.04 (s, 1H), 8.96 (d, ⁴ J=1 Hz, 1H), 8.92 (d, J=1 Hz, 1H), 8.89 (d, ⁴ J=1 Hz, 1 H), 8.24 (m, 2H), 8.15 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1H), 7.93 (dd, ³ J=6 Hz, ⁴ J=1 Hz, 1 H), 7.89-7.76 (m, ³ J=6 Hz, ⁴ J=1 Hz, 5H), 7.70 (dd, ³ J=6 Hz, J=2 Hz, 1 H), 7.66 (dd, ³ J=6 Hz, J=2 Hz, 1 H), 7.63 (dd, ³ J=6 Hz, ⁴ J=2 Hz, 1 H), 7.61 (ddd, ³ J=7 Hz, ⁴ J=2 Hz, ⁵ J=1 Hz, 1 H), 7.57(d, ³ J=4 Hz, H), 7.19 (dd, ³ J=8 Hz, ⁴ J=2 Hz, 1 H), 7.04 (ddd, ³ J=7 Hz, 6 Hz, J=1 Hz, 1 H), 6.59 (d, ³ J=8 Hz, 1 H), 3.21 (m, 24H), 1.63 (m, 24H), 1.38 (sextet, ³ J=7 Hz, 24H), 0.98 (t, ³ J = 7 Hz, 36H). ¹³ C NMR (CD ₃ OD): 200.7, 84.8, 168.0, 159.3, 158.7, 158.3, 156.8, 155.3, 151.5, 151.3, 150.3, 148.0, 141.7, 140.6, 137.6, 137.3, 127.9, 127.5, 127.2, 127.0, 126.8, 124.3, 124.2, 124.1 , 124.0, 123.8, 123.7, 122.1 , 20.7, 59.6, 24.9, 20.9, 14.1. HR S (ESI): m/z = 854.04918 [(M - 3Bu N ⁺ + 4H ⁺ ) ⁺ ] (calcd for RuC^eNsOgS*: m/z = 854.04947). Anal. Calcd. for RuC ₈ 8H ₁₄₆ N ₈ 0 ₁₇ S + 8H20: C, 61.40; H, 8.55; N, 6.51. Found: C, 61.07; H, 7.89; N, 6.44.

Physical Methods

Routine H and ¹³ C NMR spectra were recorded at 400 and 100 MHz, respectively, on a Bruker AV 400 instrument at ambient temperature unless otherwise stated. Elemental analysis (EA), electrospray ionization mass spectrometry (ESI-MS), matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF), and electron impact (El) mass spectrometry data were collected at the University of Calgary. Electrochemical measurements were performed under anaerobic conditions with a Princeton Applied Research Versa- Stat 3 potentiostat using dry solvents, Pt working and counter electrodes, a Ag pseudoreference electrode, and 0.1 MNBu ₄ BF ₄ supporting electrolyte. Electronic spectroscopic data were collected on MeOH solutions using a Cary 5000 UV-vis spectrophotometer (Varian). Steady-state emission spectra were obtained at room temperature using an Edinburgh Instruments FLS920 Spectrometer equipped with a Xe900 450W steady state xenon arc lamp, TMS300-X excitation monochromator, TMS300-M emission monochromator,

Hamamatsu R2658P PMT detector and corrected for detector response. Lifetime measurements were obtained at room temperature using an Edinburgh Instruments FLS920 Spectrometer equipped with Fianium SC400 Super Continuum White Light Source, Hamamatsu R3809U-50 Multi Channel Plate detector and data were analyzed with Edinbrugh Instruments F900 software. Curve fitting of the data was performed using a nonlinear least-squares procedure in the F900 software. DFT Calculations

Density functional theory (DFT) calculations were carried out using B3LYP (Becke, A. D. J. Chemc. Phys. 1993, 98, 5648-5652) (Becke's three-parameter exchange functional (B3) and the Lee- Yang-Parr correlation functional (LYP)) and the LanL2DZ basis set (Hay, P. J. and Wadt, W. R. J. Chem. Phys. 1985, 82, 299-310). All geometries were fully optimized in the ground states (closed shell singlet So). Time-dependent density functional theory (TDDFT) calculations were performed with IEFPCM salvation model (MeCN) using a spin-restricted formalism to examine low- energy excitations at the ground-state geometry. All calculations were carried out with the Gaussian 03W software package.

RESULTS - EXAMPLE 1

Synthesis and Structural Characterization

Cyclometalated Ru(ll) complexes of the form [Ru(dcbpyH ₂ )2(C ^A N)] ⁺ can be accessed using one of these two general routes: (i) initial coordination of the dcbpyH ₂ ligands to the Ru center followed by cyclometalation; or (ii) initial activation of the C-H bond to furnish a cyclometalated Ru site with subsequent coordination of the dcbpyH2 ligands. While the first method is typically employed to isolate compounds of type [Ru(N ^A N)2(C ^A N)] ⁺ , the latter approach has been shown to converge on a number of heteroleptic Ru(ll) and Ir complexes. The syntheses described in this study follow this latter approach because it generates high yields under mild reaction conditions and eliminates the occurrence of undesirable isomerization products when

Ru(dcbpyH ₂ )2CI ₂ is utilized as a synthon. The installation of various substituents (e.g., -N0 ₂ , -4-phenyl, -4-pyridine, -thiophene-2-carbaldehyde) on the cyclometalating 2- phenylpyridine ligand was achieved in moderate to high yields using standard Negishi or Suzuki cross-coupling reaction conditions. Noting that [(r) ⁶ -C6H ₆ )RuCl2] ₂ has been documented to be a useful precursor in cyclometalation reactions, requisite C-H activation of the cyclometalating ligands was carried out using [(rj ⁶ -p-cymene)RuCI ₂ ]2. The reaction workup can be carried out in ambient conditions, which contrasts with the anaerobic conditions required for reactions involving [(n ⁶ -C ₆ H ₆ )RuCl2] ₂ . For all of the ligands used in this study, the reaction generated a solution containing two products, [(n ² -p-cymene)Ru-(MeCN) ₂ (L#)]PF ₆ and [Ru(MeCN) ₄ (L#)]PF ₆ . Monitoring the reaction by 1 H NMR spectroscopy indicates that [(r) ² -p-cymene)Ru(MeCN) ₂ (L#)]PF ₆ is formed initially, and is progressively converted to [Ru(MeCN) ₄ (L#)]PF ₆ over the course of the reaction. Both of these species afford the respective target metal complex when combined with 2 equiv of dcbpyH ₂ ; however, greater emphasis was placed on ensuring that [(q ⁶ -p-cymene)-RuCl2]2 was completely consumed rather than separating the two intermediate species. Therefore the synthesis and characterization details for these precursors are not offered. The target complexes were obtained in reasonably high yields after refluxing the corresponding precursor mixtures with NaOH and dcbpyH ₂ in degassed (aqueous) methanol. The fully protonated forms of complexes 1-5 were isolated by the dropwise addition of HPF6 to the reactive mixture until the products precipitated out of solution; acidification of 7, 8, and 9 with HN0 ₃ produced zwitterionic compounds rather than the respective NO3 - salts.

The structural identities of the compounds were verified by a combination of elemental analysis, MALDITOF, ESI-MS, ¹ H NMR, and/or ¹³ C NMR spectroscopy. The signature upfield doublet observed at 6.39 ppm in the H NMR spectrum of 1 ,

emanating from the proton adjacent to the Ru-C bond, did not always serve as a useful spectroscopic handle because it is, in certain cases, drawn downfield to overlap with the other aromatic signals. Because of inherent solubility issues, compounds 1, 3, 6-9 were deprotonated by adjusting the pH to 7 using NBu ₄ OH; these hygroscopic compounds are all soluble in polar organic solvents. HNMR spectroscopy and elemental analysis were used to establish that 3a is fully deprotonated, and that 1a, 7a-9a all contain three NBu ₄ ⁺ counterions. This disparity is ascribed to the stronger electron-withdrawing character of the-N0 ₂ group lowering the pKa of the acid modalities. Diastereomers of complexes 7a-9a were not observed because poor solubility precluded the collection of NMR data in solvents (e.g., hexanes, chloroform) that restrict proton exchange. Thermogravimetric and elemental analysis data collectively confirm the hygroscopic nature of the deprotonated complexes (no less than 5H ₂ 0 molecules are present in solid samples of 7a-9a).

Electrochemical Properties

The electrochemical behavior of 1-5 in DMF was determined by cyclic voltammetry. Solubility issues precluded the collection of satisfactory voltammograms 7-9; thus, deprotonated forms of select compounds (i.e., 1a, 3a, 7a-9a) were prepared to facilitate a comprehensive comparison of the series. Relevant redox couples are collected in Table 1.

The voltammograms for all of the complexes reveal a reversible one-electron metal-based oxidation process and a series of reduction processes. Compound 1a exhibits a single reversible wave ascribed to the one-electron reduction of a dcbpy ligand. For the -NO2 series 2-5, the cathodic sweep leads to the reduction of the -NO2 group of the C ^A N ligand. Compound 5, which contains two -N0 ₂ groups, exhibits a reduction potential about 0.23V lower than those containing a single -N0 ₂ group. Inspection of 2-4 indicates the complexes are most easily oxidized when the -NO2 groups are meta to the organometallic bond: the additional -N0 ₂ group for 5 leads to an oxidation potential that is anodically shifted by an additional -100 mV relative to 2- 4. The placement of the aromatic substituents para to the organometallic bond reveals progressively higher oxidation potentials for 7a-9a, respectively, thus reflecting the relative electron-withdrawing character of the substituents. Compounds 7a-9a exhibit a single reversible reduction wave at comparable potentials consistent with the reduction of the dcbpy ligands.

Electronic and Fluorescence Spectroscopy

The spectral profile for each compound studied contains three broad absorption bands in the visible region centered at roughly 540, 490, and 400 nm (maxima are denoted as A _max -i , Am _ax2 , and respectively, in Figure 2) along with intense intraligand (ττ-π*) transitions below 350 nm. Representative UV-vis absorption spectra are depicted in Figure 2. The two low-energy bands are superimposed in the cases of 3a, 4, and 5. The bands in the visible region for all of the compounds are ascribed to a collection of mixed-metal/ligand to ligand charge-transfer transitions arising from a HOMO involving both the metal and the anionic portion of the CN ligand.

Electrochemical measurements indicate that significant electron density is situated on the metal; thus, these transitions are, for the sake of brevity, defined herein as metal- to-ligand charge transfer (MLCT).

The maxima for the lowest-energy MLCT bands are found over the 532-575 nm range for the series 1-5. There is a direct correlation between the number of -N0 ₂ groups present and A _ma x values, namely, the A _max i values are found at the lowest energy for 1 and the highest energy for 5, while the monosubstituted nitro derivatives 2-4 exhibit intermediate A _max1 values. The A _ma x3 values adhere to this same trend. Data for 3 reveals a lower A _ma xi value relative to the compounds where the -N0 ₂ group is situated meta to the organometallic bond. This trend is consistent with enhanced π- electron conjugation for 3 leading to a lower-energy HOMO level relative to the cross- conjugated systems 2 and 4. The molar extinction coefficients (ε) are found to range from 1 10 ⁴ - 2 x 10 ⁴ M ^"1 cm ^"1 over the series. The ε value of 0.9 ^χ 10 ⁴ M ^~1 cm ^"1 for the signal at A _max for 2 is less than half that of 3 or 4 (ε=1.9 * 10 ^"4 M ^"1 cm ^'1 ). The diminished intensity of this band is presumably a consequence of the loss of conjugation in 2 arising from steric interactions between the H atom on the adjacent pyridyl ring and the -N0 ₂ group. Compound 4 is not subject to this steric

encumbrance; thus, the -N0 ₂ group can reside in the plane of the aromatic rings of the C ^A N ligand.

The UV-vis data for the deprotonated analogues 7a-9a reveal that the lowest- energy transitions occur at 563, 556, and 550 nm, respectively. The relative intensities of the three maxima in the visible region indicate that the ε value for A _max i and A _max3 increases for 7a-9a, respectively. A hypsochromic shift of the Ama i and Amax2 values is observed with progressively stronger electron- withdrawing groups (EWGs). This trend reflects a diminished level of ττ-backbonding to dcbpyH ₂ as the aromatic moiety of the C ^A N ligand becomes more electron withdrawing. The increasing ε for A _maX 3 is the result of an increasing number of transitions to the C ^A N ligand and enhanced conjugation between the adjacent aromatic rings (vide infra). The A _maX 3 band is more intense with increasing electron-withdrawing character of the aromatic substituent. Consequently, 9a exhibits the greatest absorption envelope in the visible region of any of the compounds studied herein. Complexes containing -F groups or substituents installed para to the Ru-C bond are all weakly emissive when excited at wavelengths corresponding to A _max i , and display lifetimes over the 2-40 ns range.

TD-DFT Calculations

TD-DFT calculations were carried out on geometry-optimized structures of the metal complexes using a B3LYP/Lanl_2DZ level of theory to qualitatively assess the frontier molecular orbitals. The low level of symmetry within these systems leads to a relatively complicated orbital structure and an increase in the number of allowed electronic transitions (hence the broader absorption profiles). The predicted low- energy transitions are blue-shifted approximately 5-9 nm compared to the

experimental values listed in Table 1.

An evaluation of the electronic transitions by TD-DFT indicates that the low- energy excitation bands arise from a set of mixed-metal/ligand-to-ligand charge- transfer transitions from the predominantly metal-based dxz, dyz, d _xy orbitals to a set of ΤΓ* orbitals with exclusively dcbpyH ₂ character. Although numerous transitions comprise each of the three absorption bands in the visible region for all of the complexes, a reduction of the TDDFT results reveals some overarching trends. The lowest energy band A _ma xi, for instance, involves excited states localized primarily to the TT* system of the dcbpyH ₂ ligand cis to the anionic fragment of the C ^A N ligand. Absorption band A _max2 arises from the population of the ττ ^* orbitals of the dcbpyH ₂ ligand trans to the phenyl ring bound to the Ru site, while the higher energy band at about 400 nm (A _maX 3) involves a more significant participation of the ττ ^* orbitals belonging to the C ^A N ligand. Anomalous behavior is observed for 3 because the low- lying empty orbitals contain more C ^A N character.

The dominant allowed transitions that comprise the lowest-energy absorption band, A _max i , are depicted schematically for 3, 7 and 9 in Figure 3. The d^, dxy and dxz orbitals comprise the three highest occupied molecular orbitals for compounds 1-5, 7- 9; however, they are not degenerate because of the Ci symmetry. For complex 8, the HOMO-1 orbital is situated solely on the pendant pyridine moiety, and the d^ and d^ orbitals are found at the HOMO-2 and HOMO-3 levels. In general, the HOMO is a linear combination of the metal d^ orbital and the anionic phenyl ring of the C ^A N ligand with empty low-lying orbitals extended over the ττ ^* system of the dcbpyH ₂ ligands. For 2, 4, and 5, however, the lowest energy excited states are localized to the phenyl ring and the -NO2 group(s) of the C ^A N ligand. For 3, where the -NO2 group is para to the organometallic bond, the lowest unoccupied levels involve both the dcbpyH ₂ ligands and the nitrophenyl scaffold; the HOMO is a mixture of the d^ orbital and nitrophenyl moiety.

The addition of aromatic substituents to the C ^A N ligand results in an expansion of the HOMO to include the phenyl, 4-pyridine, and thiophene-2-carbaldehyde moieties in 7-9, respectively. There is an enhancement of orbital character over the aromatic scaffold of 9 compared to 7 and 8 because of the relatively small dihedral angle between the phenyl group of the C ^A N ligand and the thiophene substituent. Electronic transitions comprising the low energy excitation MLCT band for 7-9 occur from the metal d^, d^, d^ orbitals to LUMOs localized to the dcbpyH ₂ ligands; the C ^A N TT* orbitals are found to be 1.4, 1.4, and 0.7 eV higher in energy than the LUMO in 7-9, respectively. EXAMPLE 2

This example describes the synthesis and testing of compound 10. Compounds 11 and 12 are baseline materials used as a reference point for the comparison of the performance of compound 10. PREPARATION OF EXAMPLE 2 COMPOUNDS

All manipulations were performed using solvents passed through an MBraun solvent purification system prior to use; chloroform (CHCI ₃ ) and tetrahydrofuran (THF) solvents were analytical grade (without stabilizer). All reagents were purchased from Aldrich unless otherwise stated. 1-bromo-2,4-bis(trifluoromethyl)benzene was purchased from Oakwood Chemical and Pd(PPh ₃ ) ₄ from the Pressure Chemical Company. [Ru(C ₆ H ₆ )Cl2]2, ²¹ 4,4'-diethylester-2,2'-bipyridine (deeb), ²² 4,4'-dicarboxy- 2,2'-bipyridine (dcbpyH ₂ ), ²² 4,4'-dibromo-2-2'-bipyridine, ²³ 2-bromo-5-hexylthiophene, ²⁴

1- butyl-3-methylimidazolium iodide ⁵ [Co(bpy) ₃ ](PF ₆ )2, ²⁶ [Co(bpy) ₃ ](PF ₆ ) ₃ , ²⁶ complexes 12-13 ²⁷ were prepared as previously reported. Purification by column chromatography was carried out using silica (Silicycle: Ultrapure Flash Silica) and basic alumina (Fluka). Analytical thin-layer chromatography (TLC) was performed on aluminum-backed sheets pre-coated with silica 60 F254 adsorbent (0.25 mm thick; Merck, Germany) or with plastic-backed sheets pre-coated with basic alumina 200 F254 adsorbent (0.25 mm thick, Selecto Scientific: Georgia, USA) and visualized under UV light. H NMR chemical shifts (δ) are reported in parts per million (ppm) from low to high field and referenced to residual non-deuterated solvent. Standard abbreviations indicating multiplicity are used as follows: s = singlet; d = doublet; t = triplet; m = multiplet. Labeling scheme for ¹ H NMR assignments for all compounds follows. Elemental analysis (EA), electrospray ionization (ESI) mass spectrometry data were collected at the University of Calgary.

2- (5-hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (PL10)

A degassed THF solution ( 25 mL) containing 2-bromo-5-hexylthiophene (4280 mg, 7.32 mmol) was cooled to -70° C at which point n-butyllithium (8.31 mL, 20.8 mmol) was added dropwise while maintaining the temperature at -70 °C. After the reaction was stirred at this temperature for 45 min, 2-isopropoxy-4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolane (5.30 mL, 26.0 mmol) was added. The reaction was brought to 25 °C and then stirred for 18 h. The addition of methanol (15 mL) turned the reaction opaque white before returning to a clear, colourless solution. The reaction was filtered and solvent removed in vacuo. The crude product was purified using a Si0 ₂ plug (hexanes/Ch^C ; 3:1 ; v.v) to produce a yellow oil in quantitative yield. H NMR

(CDCI3): δ 7.49 (d, 1 H, ³ J = 3.4 Hz, H _b ), 6.87 (d, 1 H, ³ = 3.4 Hz, H _a ), 2.87 (t, 2H, H _c ), 1.70 (quintet, 2H, H _d ), 1.34 (m, 18H, H _e , _f,g ,i), 0.90 (m, 3 H, H _h ). ³ C NMR (CDCI ₃ ): δ 153.8, 137.5, 125.9, 83.9, 82.9, 31.8, 31.7, 30.3, 28.9, 24.8, 22.7, 14.2. 4,4'-bis(5-hexylthiophen-2-yl)-2,2'-bipyridine (dthbpy)

A previously reported synthesis was modified as described here ²⁸ . To a degassed THF/H ₂ 0 (9:1 v:v, 50 mL) solution containing PL10(2504 mg, 8.50 mmol), 4,4'-dibromo-2,2'-bipyridine (1069 mg, 3.404 mmol) and K ₂ C0 ₃ (694 mg, 5.03 mmol) was added Pd(PPh ₃ ) ₄ (471 mg, 0.408 mmol). The reaction was heated at reflux for 40 h, cooled and then washed with CH ₂ CI ₂ (3 χ 30 mL). The organic fractions were combined and dried over MgS0 ₄ and filtered. The crude product that was obtained after solvent removal was purified using a Si0 ₂ plug [CH ₂ CI ₂ followed by EtOAc] to yield 768 mg (46.1 %) of an off-white solid. Characterization data matches that which was previously reported. ²⁸

2-(2,4-bis(trifluoromethyl)phenyl)pyridine (ppy-(CF ₃ ) ₂ )

After a THF solution (25 mL) containing 1-bromo-2,4- bis(trifluoromethyl)benzene (391 1 mg, 13.35 mmol), 2-pyridylzinc bromide (2840 mg, 2.71 mmol) and Pd(PPh ₃ ) ₄ (881 mg, 0.763 mmol) was heated at reflux for 24 h, an additional quantity of Pd(PPh ₃ ) ₄ (444 mg, 0.384 mmol) was added to the reaction mixture and left to reflux for another 18 h. The cooled solution was washed with saturated NaHC0 _3(aq) (40 mL) and EDTA (40 mL), respectively. The aqueous layers were combined and washed with Et ₂ 0 (3 χ 30 mL). All organic fractions were then combined, dried with gS0 ₄ and solvent removed in vacuo to produce the crude product as a yellow oil. Further purification by column chromatography [Si0 ₂ ; CH ₂ CI ₂ ; R _f = 0.23] yielded 761 mg (20.6%) of the product as a light yellow oil. H NMR (CDCI ₃ ): δ 8.60 (ddd, 1 H, ³ J = 4.9 Hz, J = .7 Hz, ⁵ J = 0.9 Hz, H _a ), 7.96 (s, 1 H, H _e ), 7.77 (d, H, ³ J = 8.1 Hz, Hi), 7.64 (dt, 1 H, ³ J = 7.7 Hz, ⁴ J = 1.7 Hz, H _c ), 7.57 (d, 1 H, ³ J = 8.1 Hz, H _d ), 7.35 (d, 1 H, ³ J = 7.9 Hz, H _g ), 7.21 (dd, 1 H, ³ J = 7.6, 4.9 Hz, H _b ). ¹³ C NMR (CDCI ₃ ): δ 170.8 (s, 1 C), 156.3 (s, 1 C), 149.3 (s, 1 C), 143.6 (s, 1 C), 136.1 (s, 1 C), 132.4 (s, 1 C), 130.7 (q, 1 C, ² J = 33.5), 129.2 (q, 1 C, ² J = 31.6), 128.3 (m, 1C), 123.7 (m, 1 C), 123.5 (m, 1C), 123.4 (q, 1 C, ¹ J = 272.0), 123.0 (s, 1 C), 120.6 (q, 1 C, V = 274.1 ) HRMS (ESI): mlz = 292.055965 [M ⁺ ] (calcd for [C ₁₃ H ₈ F ₆ N] ⁺ : mlz = 292.055545).

[Ru(CH ₃ CN)4(ppy-(CF ₃ ) ₂ )][PF6] (P10)

To a flask containing [Ru(C ₆ H ₆ )CI ₂ ]2 ( 72 mg, 0.343 mmol), NaOH (28 mg, 0.70 mmol) and KPF ₆ (253 mg, 1 .37 mmol) was added a solution of ppy-(CF ₃ ) ₂ (203 mg,

0.680 mmol) in degassed MeCN (7 mL). The reaction was heated at 45 °C for 45 h, filtered and then the solution was passed through a column [Al ₂ 0 ₃ (basic):

C^C / eCN, 9:1]. The first yellow band was isolated to yield 624 mg (88.1 %) of the yellow solid product. H NMR (CD ₃ CN): δ 9.15 (ddd, 1 H, ³ J = 5.7 Hz, ⁴ J = 1.7 Hz, ⁵ J = 0.7 Hz, i), 8.53 (s, H, H _a ), 8.23 (d, 1 H, ² J = 8.5 Hz, H _e ), 7.85 (ddd, 1 H, ³ J = 9.2, 7.5 Hz, ⁴ J = 1.7 Hz, M), 7.58 (s, 1 H, H _c ), 7.33 (ddd, 1H, ³ J = 7.1 , 5.7 Hz, ⁴ J = 1.2 Hz, H _g ), 2.52 (s, 3H, Ha _' ), 2.01 (s, 6H, c), 1.96 (s, 3H, H _z ). HRMS (ESI): m/z = 5 5.026522 [M ⁺ - CH ₃ CN] (calcd for [RuC ₁₉ Hi5F ₆ N ₄ ] ⁺ : mlz = 515.02444). Anal, calcd. for

RuC ₂ iHi ₈ F _{6 5} PF ₆ : C, 36.01 ; H, 2.59; N, 10.00. Found: C, 36.66; H, 2.63; N, 9.74.

[Ru(dthbpy)(deeb)(ppy-(CF ₃ ) ₂ )][PF ₆ ] (I10)

An absolute ethanolic solution (100 mL) of deeb (214 mg, 0.713 mmol) and dthbpy (349 mg, 0.713 mmol) was heated at 70 °C until both ligands dissolved and subsequently cooled to room temperature. P10 (501 mg, 0.713 mmol) was added to the solution and the reaction mixture was heated at reflux for 30 min. Upon cooling the mixture and removing solvent in vacuo, the solid reaction mixture was purified by column chromatography [Si0 ₂ ; (CH ₂ CI ₂ /MeCN 98:2); R _f = 0.54] and isolated to afford 300 mg (31.6%) of the product as a purple solid. H NMR (CD ₃ OD): δ 9.1 1 (d, 1 H, ⁴ J = 0.9 Hz, M), 9.03 (d, 1 H, ⁴ J = 1.3 Hz, H _s ), 8.78 (d, 1H, ⁴ J = 1.8 Hz, H _m ), 8.77 (d, H, ⁴ J = 1.8 Hz, M), 8.41 (d, 1 H, ³ J = 8.4 Hz, H _e ), 8.17 (d, 1 H, ³ J = 5.9 Hz, H,), 8.15 (d, 1H, ³ J = 5.0 Hz, Wv). 8.02 (dd, 1 H, ³ J = 5.7 Hz, ⁴ J = 1.6 Hz, H _u ), 7.79 (m, 5H, M, _h ,r,w, _y ), 7.54 (d, H, ³ J = 5.9 Hz, M), 7.52 (d, 1 H, ³ J = 5.8 Hz, H _p ), 7.50 (s, 1H, M), 7.45 (m, 2H, Η _ια ), 7.14 (s, H, Ha), 7.11 (ddd, 1H, ³ J = 7.2 Hz, ⁴ J = 5.7 Hz, ⁴ J = 1.2 Hz, H ₉ ), 6.91 (m, 2H, H _x ,z), 4.47 (m, 4H, H _g ), 2.86 (m, 4H, H _a ), 1.71 (m, 4H, Μ>·). 1 -45-1.31 (m, 18H, M. _d . e', h , 0.90 (m, 6H, M). ¹⁹ F NMR (CD ₃ OD): δ -58.6 (s, -CF ₃ ), -64.6 (s, -CF ₃ ), -74.8 (d, ² J _P-F = -707.9 Hz, -PF ₆ ) . MS (ESI): mlz = 1 180.1 [M ⁺ ] (calcd for mlz = 1 180.3). Anal, calcd. for RUC55H50F6N5O4S2: C. 53.47; H, 4.41 ; N, 5.28. Found: C, 53.34; H, 4.36; N, 5.19.

Ru(dthbpy)(dcbpyH)(ppy-(CF ₃ ) ₂ ) (10)

A DMF/H ₂ 0/NEt ₃ solution (3:1 :1 v.v.v, 30 mL) containing 110 (289 mg, 0.218 mmol) was heated at reflux for 16 h. Subsequent removal of solvent under reduced pressure left 182 mg (74.3%) of the product as a purple solid. ¹ H NMR (CD ₃ OD): δ 9.03 (s, 1 H, M), 8.96 (s, 1 H, W ₈ ), 8.75 (d, 1 H, ⁴ J = 1.8 Hz, H _m ), 8.74 (d, 1 H, J = 1.8 Hz, M), 8.39 (d, 1 H, ³ J = 8.4 Hz, H _e ), 7.92 (m, 2H, H _q , _v ), 7.86 (m, 2H, M, _u ), 7.80 (ddd, 1H, ³ J = 8.6 Hz, 7.5 Hz, ⁴ J = 1.7 Hz, M), 7.76 (d, 1 H, ³ J = 3.7 Hz, H _w ), 7.75 (d, 1 H, ^Z J = 3.7 Hz, M _y ), 7.63 (dd, 1 H, ³ J = 5.8 Hz, ⁴ J = 1.7 Hz, M), 7.58 (d, 1H, ³ J = 5.9 Hz, M), 7.56 (d, 1H, ³ J = 5.6 Hz, H _p ), 7.46 (m, 2H, H _Ci0 ), 7.41 (dd, 1 H, ³ J = 6.1 Hz, ⁴ J = 2.0 Hz, H), 7.18 (s, 1H, H _a ), 7.1 1 (ddd, 1 H, ³ J = 7.2 Hz, J = 5.7 Hz, ⁴ J = 1.2 Hz, H _g ), 6.90 (m, 2H, «x _,z ), 2.86 (m, 4H, Η _Β ·), 1.71 (m, 4H, Hf), 1.40 (m, 4H, H _c , 1.33 (m, 8H, H _d ., _e ), 0.90 (m, 6H, H _f ). ¹⁹ F NMR (CD ₃ OD): δ -58.5 (s, -CF ₃ ), -64.5 (s, -CF ₃ ). MS (ESI): m/z = 1124.1 [M ⁺ ] (calcd for [RuCssHsoFe sO^]*: mlz = 1 124.2). Anal, calcd. for

RuCssHsoFeNgC Sz: C, 58.81 ; H, 4.40; N, 6.24. Found: C, 58.53; H, 4.36; N, 6.09. Physical Methods

D and 2D ¹ H and ¹³ C spectra were recorded at 400 MHz and 100 MHz, respectively, on a Bruker AV 400 instrument at ambient temperature unless otherwise stated. Electrochemical measurements were performed under anaerobic conditions with a Princeton Applied Research VersaStat 3 potentiostat using dry solvents, Pt working and counter electrodes, a Ag psei doreference electrode, and a 0.1 M

NBu ₄ BF ₄ supporting electrolyte. Electronic spectroscopic data were collected on MeOH solutions using a Cary 5000 UV-vis spectrophotometer (Varian). Steady-state emission spectra were obtained at room temperature using an Edinburgh Instruments FLS920 Spectrometer equipped with a Xe900 450W steady state xenon arc lamp, TMS300-X excitation monochromator, TMS300-M emission monochromator,

Hamamatsu R2658P PMT detector and corrected for detector response. Lifetime measurements were obtained at room temperature using an Edinburgh Instruments FLS920 Spectrometer equipped with Fianium SC400 Super Continuum White Light Source, Hamamatsu R3809U-50 Multi Channel Plate detector and data were analyzed with Edinburgh Instruments F900 software. Curve fitting of the data was performed using a non-linear least squares procedure in the F900 software.

Cell Fabrication

Photoanodes were prefabricated by Dyesol, Inc. (Australia) with a screen- printable Ti0 ₂ pastes (18-NRT and WER4-0, Dyesol™). The active area of the Ti0 ₂ electrode is 0.28 cm ² with a thickness of 12 μΐτι (18-NRT) and 3 μιη (WER4-0) on fluorine-doped tin-oxide [FTO; TEC8 (8 Ω cm ^"2 )]. T1O ₂ substrates were treated with TiCI ₄ (aq) (0.05 M) at 70 °C for 30 min and subsequently rinsed with H ₂ 0 and then dried prior to heating. The electrodes were heated to 450 °C for 20 min in an ambient atmosphere and allowed to cool to 80 °C before dipping into the dye solution. The anode was soaked overnight for 16 h in an ABS EtOH solution containing dye (~0.25 mM), coadsorbent chenodeoxycholic acid (-2.5 mM) and Bu ₄ NOH (1 eq). The stained films were rinsed copiously with ABS EtOH and dried. The cells were fabricated using Pt-coated counter-electrode [FTO TEC-15 (15 Ω cm ^"2 )] and sealed with a 30 μιη Surlyn (Dupont) gasket by resistive heating. An acetonitrile based electrolyte solution EL1 : (0.6 M butylmethylimidazolium iodide, 0.06 M l ₂ , 0.1 M Nal, 0.1 M guanidinium thiocyanate and 0.5 M ierf-butylpyridine in acetonitrile) or EL2: (0.21 M

[Co(bpy) ₃ ](PF ₆ ) ₂ , 0.033 M [Co(bpy) ₃ ](PF ₆ ) ₃ , 0.1 M NaCI0 ₄ and 0.2 M terf-butylpyridine in acetonitrile) was introduced to the void via vacuum backfilling through a hole in the counter electrode. In the case of EL1 , the hole was sealed with an aluminum-backed Bynel® foil (Dyesol™). In the case of EL2, the hole was covered with a microscope slide and sealed with epoxy. A strip of aluminum-backed Bynel® was adhered to the microscope slide. After sealing, silver bus bars were added to all cells.

Dye Characterization

E(S ⁺ /S*) calculated using E(S ⁺ /S*) = E(S ⁺ /S)-E ₍₀ -o) where E _(0- o) is obtained from the higher energy side of corrected emission band where the intensity is ca. 10% of the maximum. ¹⁰

Cell Characterization.

Photovoltaic measurements were recorded with a Newport Oriel solar simulator

(Model 9225A ) equipped with a class A 150 W xenon light source powered by a Newport power supply (Model 69907). The light output (area = 5 cm χ 5 cm) was calibrated to AM 1 .5 using a Newport Oriel correction filter to reduce the spectral mismatch in the region of 350-700 nm to less than 1.5%. The power output of the lamp was measured to 1 Sun (100 mW cm ^'2 ) using a certified Si reference cell.

Neutral density filters were used to achieve lamp outputs between 10-100 mW cm ^"2 . The current-voltage (l-V) characteristic of each cell was obtained by applying an external potential bias to the cell and measuring the generated photocurrent with a Keithley digital source meter (Model 2400). All cells were measured with a mask size of 0.13 cm ² . IPCE measurements were performed on a QEX7 Solar Cell Spectral Response Measurement System from PV Instruments, Inc. The system was calibrated with a photodiode that was calibrated against NIST standard I755 with a transfer uncertainty of less than 0.5% between 400-1000 nm, and less than 1 % at all other wavelengths. All measurements were made in AC mode at a 10-Hz chopping frequency under a bias light. The system was calibrated and operated in Beam Power mode. Electrochemical impedance spectroscopy (EIS) was measured on a Gamry EIS300 potentiostat. All EIS measurements were performed in the dark and scanned a frequency range from 100 kHz to 0.5 Hz with a 10-mV voltage modulation applied to the bias.

DFT Calculations

The Gaussian 03 computational package ²⁹ to perform ground state geometries optimization calculations employing the Becke's three-parameter hybrid exchange functional and the Lee-Yang-Parr nonlocal correlation functional B3LYP ^30"32 and LANL2DZ basis set ^{33 3} with an effective core potential for Ru and a 6-31 G* basis set was used for F, S, C, N, O and H atoms. ³⁵ TDDFT calculations were also performed using this methodology and the first 60 excited states were calculated. The

calculations by first-principles method were used for obtaining the accurate excitation energies and oscillator strengths. We modeled the solvent with the PCM model using methanol as solvent. ³⁶

RESULTS - EXAMPLE 2

In this example, complex 10, a Ru" complex devoid of NCS ^" groups and bearing aliphatic substituents that can generate high efficiencies in a conventional DSSC, was prepared. Complex 10 was found to produce exceptional cell performance for a Ru-based dye with a Co-based electrolyte at 1 sun. Complex 10 was obtained using a synthetic approach similar to that for 12 and 13, the scheme being shown in Figure 6. ²⁷ Briefly, the cyclometalating ligand, ppy-(CF ₃ )2, which was synthesized by a Negishi coupling of 2-pyridylzinc bromide and 1-bromo- 2,4- bis(trifluoromethyl)benzene, [Ru(C6H6)Cl2]2, NaOH, and KPF6 were reacted to furnish [Ru(CH ₃ CN)4(ppy-(CF ₃ )2)]PF ₆ . This complex was then treated with deeb (4,4'- diethylester- 2,2'-bipyridine) and dthbpy (2,2'-bis(5-hexylthiophen-2-yl)- 2,2'-bipyridine) to give the ethylester intermediate [Ru-(deeb)(dthbpy)(ppy-(CF ₃ )2)]PF ₆ , which affords 0 in high purity upon saponification.

The UV/Vis spectrum of 10 revealed a broader and more intense absorption envelope relative to both 12 and 11 (Figure 7). The absorption spectra of the dyes tethered to Ti0 ₂ follow similar trends, but display a less pronounced difference in intensities, presumably due to the lower surface coverage of 10 (Figure 8). Intense π- π* transitions dominate the spectrum of 10 below 350 nm, while metal-to-ligand charge-transfer transitions comprise the broad bands centered at 404 nm (ε=2.9 x 10 ⁴ M ^"1 cm ^"1 ) and 555 nm (ε=2.6 x 10 ⁴ M ^"1 cm ^"1 ). These assignments were corroborated by DFT, which predicts the two lowest-energy bands to contain transitions from a metal-based HOMO-1 level to lowest unoccupied molecular orbital (LUMO) and LUMO+1 levels that have orbital character localized to the polypyridyl ligands (Figure 9). The shoulder at approximately 660 nm for 10 is predicted by DFT to be a HOMO to LUMO transition characterized by a low oscillator strength arising from the

orthogonality of the constituent orbitals; however, this band may also be due to the direct population of the ³ MLCT state. ³⁷ The intensities of the low-energy absorption bands of 10 are relatively higher than those of 12 and 11 due to the presence of the thiophene units. Light absorption by 10 occurs beyond 700 nm even with the electron- withdrawing -CF ₃ groups present.

The cyclic voltammogram of 10 in DMF revealed a reversible one-electron oxidation at +0.99 V vs. NHE and a reversible ligand-based reduction wave at -1.17 V vs. NHE (Figure 10). (For comparison, the first oxidation potentials for 12 and 13 occur at +0.70 and +0.93 V, respectively.) The EQ-Q energy of 1.84 eV for 10 extracted from the intersection of the absorption and emission profiles enables a determination of the excited-state oxidation potential E(S+/S*) to be -0.85 V— a value that is appropriately positioned for electron injection into the Ti0 ₂ conduction band (ECB ^S - 0.5 V vs. NHE).

Photovoltaic data was recorded on DSSCs containing 10 with electrolytes relying on either the Γ/Ι3 ^" (denoted EL1 ) or Co'"/Co" (denoted EL2) redox couples (Table 2). Data for devices containing 12 and 11 are provided as a benchmark (Entries 1-2, Table 2). While the devices with EL1 reach η=6.3% for 11 , a markedly lower value was obtained for 12, which is presumably due to an oxidation potential (i.e., +0.70 V ²⁷ ) that is inappropriate for efficient dye regeneration. The higher oxidation potential (and slightly enhanced absorbance) of 10, however, lead to a stark improvement in cell performance among the series (Entry 3, Table 2; Figure 11 ). Efficiencies approaching 9% were obtained for cells measured at lower light intensities and/or without a mask (Entries 4-5, Table 2). Table 2: Photovoltaic data obtained under A 1 .5 irradiation.

Entry Dye _E| [bl Light Level ^[cl V _0C [V] J _sc [mA cm ^"2 ] FF η [%]

1 12 EL1 1 0.63 9.7 0.66 4.1

2 11 EL1 1 0.65 13.3 0.73 6.3

3 10 EL1 1 0.66 16.3 0.68 7.3

4 10 EL1 0.5 0.64 8.6 0.74 8.3

₅ M 10 EL1 0.5 0.66 9.6 0.68 8.8

₆ M 10 EL1 1 0.73 14.3 0.66 6.9

7 10 EL2 1 0.72 1 1 .8 0.64 5.5

₈ [d] 10 EL2 1 0.78 13.1 0.61 6.2

9 11 EL2 1 0.49 3.8 0.51 0.96

DSSC substrates consist of a 12 m TiC½ active layer and 3 μητι TiC^ scattering layer unless otherwise specified. ^lbJ EI=electrolyte; EL1 : BMII (1 -butyl-3-methylimidazolium iodide) (0.6 M), l ₂ (0.06 M), Nal (0.1 M), /BP (4-terf-butylpyridine) (0.5 M), GuSCN (guanidinium thiocyanate) (0.1 m) in MeCN; EL2: [Co(bpy) ₃ ](PF ₆ ) ₂ (0.21 M), [Co(bpy) ₃ ](PF ₆ ) ₃ (0.033 M), NaCI0 ₄ (0.1 M), fBP (0.2 M) in MeCN.

[c] Light intensity measured in suns. M Data recorded on same cell as previous entry without a mask. [e]

Substrate consists of a 6 μηι T1O2 active layer and 3 μιη T1O2 scattering layer.

The superior cell performance of 10 is manifested in the higher short-circuit photocurrent density (J _sc ; 16.3 mA cm ^"2 ), which arises from the thiophene groups enhancing the absorbance profile and the alkyl groups suppressing recombination. This explanation is supported by: 1 ) normalized incident photon-to-current efficiency (IPCE) measurements, which display an enhanced external quantum efficiency between 600-700 nm for 10 (Figure 12); and 2) Nyquist plots of cells measured in the dark at the voltage corresponding to their V _oc (Figure 13). (A transmission line model (as depicted in Figure 14) was applied to the electrochemical impedance

spectroscopy (EIS) data; the results are summarized in Table-3. ²⁰ ) For conventional cells (i.e., EL1 and a 12 μιη Ti0 ₂ active layer), the electron-transport resistance in ΤΊΟ2 was found to be highest for 12 (64 Ω) and lowest for 10 (11 Ω). Moreover, cells containing 10 had the highest resistance (30 Ω) to electron recombination with EL1 and thus the longest electron-diffusion length, L _n .

Table 3: Fitted electrochemical impedance spectroscopy data.

Dye Electrolyte L (pm) ^laJ R _s (Q R _t (Q) ^cl R _ct (Q) ^aJ R _Pt (Q) ^e) L _d (pmj^

EL1 12 + 3 13 64 28 3.6 7.9

EL1 12 + 3 14 13 25 1.5 17

EL1 12 + 3 14 1 1 30 3.0 20

EL1 6 + 3 13 2.3 33 1.0 23

EL2 12 + 3 14 19 26 1.5 14

l ^aJ L = film thickness.

^|b] R _s = cell series resistance.

^[cl R _t =∑(r _t ) = transport resistance through Ti0 ₂ .

^[d] Rct =∑(r _c t) = resistance to electron recombination with Ti0 ₂ .

^[eI Rpt = electron transfer resistance at Pt coated counter electrode.

ι ^η L _d = L(Rct/Rt)° ⁵ = normalized diffusion length.

Given the superior absorbance of 10, the performance of cells using thinner ΤΊΟ2 films was examined (Entry 6, Table 2). Despite a two-fold reduction in the film thickness of the substrate, the J _∞ was lowered by only 12% to 14.3 mA cm ^*2 . This diminution in current was countered by an 1 1% increase in V _oc to 0.73 V, which offsets the decrease in photocurrent to afford a reasonably high η value of 6.9%. EIS data indicated that the increase in V _oc emanates from lower recombination arising from improved charge collection (e.g., a low transport resistance of 2 Ω coupled to a larger charge-transfer resistance with the electrolyte of 33 Ω), thereby resulting in a cell that exhibits minor losses in performance compared to the analogous cells with thicker substrates.

Recent reports have highlighted electrolytes that rely on the Co^/Co" redox shuttle and that can produce high η values for organic dyes; ^38"40 however, a similar performance rating with Ru-based dyes at 1 sun has apparently not been reported; for example, 3.9% using the [Co(dbbip) ₂ ] ² 7 ³⁺ redox couple (dbbip=2,6-bis(1'-butylbenz- imidazol-2'-yl)pyridine) with Z907. ⁴¹ Because the electronic geometry of the HOMO for 10 differs from that of dyes bearing NCS ^" ligands (e.g., 11, Z907), the interaction with an electrolyte derived from [Co(bpy) ₃ ] ²⁺ / ³⁺ (e.g., EL2) was examined. A DSSC containing 10 reached η=5.5% (Entries 7 and 8). This is apparently the highest value obtained for a Ru-based dye with a Co-based electrolyte at 1 sun. Prior to this discovery, the highest efficiency under 1 Sun for a Ru-based dye using [Co(bpy)3] ²⁺ / ³⁺ was 1.3%; ⁴² a cell efficiency of 0.96% was obtained with 1 (Entry 9, Table 2). The high η and IPCE values (e.g., 50% over 400-600 nm) for 10 were obtained without the use of blocking layers. ^42,43 A much larger Warburg feature was observed in the EIS measurements for EL2 than for EL1 (Figure 13), which can be ascribed to mass- transport limitations. ⁴⁴ EXAMPLE 3

This example describes the synthesis and testing of compound 14.

PREPARATION OF EXAMPLE 3 COMPOUNDS

All manipulations were performed using solvents passed through an MBraun solvent purification system prior to use; chloroform (CHCI ₃ ) and tetrahydrofuran (THF) solvents were analytical grade (without stabilizer). All reagents were purchased from Aldrich unless otherwise stated. 1-bromo-2,4-bis(trifluoromethyl)benzene was purchased from Oakwood Chemical and Pd(PPh ₃ ) ₄ from the Pressure Chemical Company. 4,4'-diethylester-2,2'-bipyridine (deeb), 4,4'-dicarboxy-2,2'-bipyridine (dcbpyh ), 4,4'-dibromo-2-2 ^, -bipyridine, 1-butyl-3-methylimidazolium iodide,

[Ru(bpy)(deeb)(ppy)]PF ₆ and compounds 15 and 16 were prepared as previously reported. ^27,45,46 Purification by column chromatography was carried out using silica (Silicycle: Ultrapure Flash Silica) and Sephadex L-20. Analytical thin-layer

chromatography (TLC) was performed on aluminum-backed sheets pre-coated with silica 60 F254 adsorbent (0.25 mm thick; Merck, Germany). ¹ H NMR were carried out and lemental analysis (EA) and electrospray ionization (ESI) mass spectrometry data were collected at the University of Calgary.

N-(4-(5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)thiophe n-2-yl)phenyl)-4- (hexyloxy)-N-(4-(hexyloxy)phenyl)benzenamine (17)

A degassed THF solution (75 mL) containing 15 (785 mg, 1.29 mmol) was cooled to -78 °C at which point n-butyllithium (0.62 mL, 1.6 mmol) was added dropwise while maintaining the temperature at -78 °C. After stirring the reaction for 45 minutes, 2-isopropoxy-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (0.40 mL, 2.0 mmol) was added. The dark green reaction was warmed to 25 °C and stirred for 18 h to produce a light orange solution. The addition of MeOH (mL) turned the solution orange in colour. The solvent was removed in vacuo and the residual product redissolved in DCM and washed with H2O (3 χ 20 mL), then dried with MgS0 ₄ and filtered. The resultant product was preadsorbed on S1O2 and purified using column chromatography [Si0 ₂ ; CH ₂ CI ₂ /Hexanes, 4:1 , v.v) to remove impurities followed by EtOAc to obtain the product]. The product could not be isolated pure. The resultant mixture was used as is in subsequent reaction steps.

4,4'-di(N-(4-(5-thiophen-2-yl)phenyl)-4-(hexyloxy)-N-(4- (hexyloxy)phenyl)benzenamine)-2,2'-bipyridine (18)

A degassed THF/H ₂ 0 (9:1 , v.v, 50 mL) solution containing 17 (520 mg, 0.795 mmol), 4,4'-dibromo-2,2'-bipyridine (101 mg, 0.322 mmol), K ₂ C0 ₃ (554 mg, 4.00 mmol) and Pd(PPh ₃ ) ₄ (45 mg, 0.039 mmol) was heated at reflux for 24 h upon which a half equivalent of Pd(PPh ₃ ) ₄ (22 mg, 0.019 mmol) was added to the reaction. The reaction was heated at reflux for another 16 h and then the solvent removed in vacuo. The resultant solid was redissolved in DCM and washed with H ₂ 0 (3 20 mL), then dried with MgS0 ₄ and filtered. Hexanes were added to the filtrate to precipitate the desired product. Filtration yielded 350 mg (95.0%) of a yellow/green solid. H NMR (CDCI ₃ ): δ 8.67 (d, 2H, ³ J = 5.3 Hz, H _a ), 8.65 (d, 2H, ⁴ J = 1.7 Hz, H _c ), 7.62 (d, 2H, ³ J = 3.8 Hz, H _d ), 7.51 (dd, 2H, ³ J = 5.2 Hz, ⁴ J = 1.8 Hz, H _b ), 7.45 (d, 4H, ³ J = 8.7, H _f ), 7.23 (d, 2H, ³ J = 3.8 Hz, H _e ), 7.09 (d, 8H, ³ J = 8.9 Hz, H _h ), 6.93 (d, 4H, ³ J = 8.7 Hz, H,), 6.85 (d, 8H, ³ J = 8.9 Hz, H _g ), 3.95 (t, 8H, ³ J = 6.6 Hz, Hj), 1.79 (m, 8H, H _k ), 1.48 (m, 8H, Hi), 1.35 (m, 16H, H _m , _n ), 0.92 (m, 12H, H ₀ ). ¹³ C NMR (CDCI ₃ ): 156.1 , 149.2, 140.4, 132.4, 132.3, 132.1 , 132.1 , 128.8, 128.7, 127.1 , 126.7, 125.7, 123.1 , 120.2, 119.8, 117.3, 1 5.6, 68.5, 31.8, 29.6, 26.0, 22.8, 14.2. HRMS (ESI): m/z = 1207.61370 i(M+H) ⁺ ] (calcd for [078^7^0482]+: m/z = 1207.61687).

[Ru(18)(deeb)(ppy(CF ₃ ) ₂ )]PF6 (19)

To a 3:1 ABS EtOH/CHCI ₃ mixture containing deeb (77.6 mg, 0.259 mmol) and 18 (312 mg, 0.259) was added 16 (181 mg, 0.259 mmol). The reaction mixture was heated at reflux for 1.5 h to produce a dark brown solution. After solvent removal in vacuo the resultant solid was purified by column chromatography [S1O2; DCM/MeCN (96:4); Rf = 0.6] and isolated to afford 267 mg (52.5%) of a brown solid. ¹ H NMR

(CDCI3): δ 9.00 (s, 1H, d, 8.93 (s, 1H, H _s ), 8.35 (m, 3H, H _e ,, _,m ), 8.11 (d, 1H, ³ J = 6.1 Hz, H _q ), 8.03 (d, 1 H, ³ J = 5.6 Hz, H _v ), 7.83 (m, 2H, H,J, 7.71 (dd, 1 H, ³ J = 5.7 Hz, ⁴ J = 1.1 Hz, H _h ), 7.65 (m, 3H, H _r>w , 7.55 (s, 1 H, H _c ), 7.47 (d, 1 H, ³ J = 6.2 Hz, H), 7.43 (d, 1 H, ³ J = 6.1 Hz, H _p ), 7.30 (m, 6H, Η _0ιβ · _β ·), 7.18 (m, 3H, H _a , _XiZ ), 7.06 (ddd, 1 H, ³ J = 7.8 Hz, 5.9 Hz, ⁴ J = 1.0 Hz, H ₉ ), 6.93 (d, 4H, ³ J = 8.9 Hz, H _d ' _{0r d} ^» ), 6.92 (d, 4H, ³ J = 8.9 Hz, 6.77 (d, 4H, ³ J = 8.9 Hz, H _c -or c), 6.76 (d, 4H, ³ J = 8.9 Hz, _c ^> „<<·), 6.67 (d, 2H, ³ J = 8.5 Hz, H _b - _{or b} ^» ), 6.65 (d, 2H, ³ J = 8.6 Hz, H _b - _{or b} ^» ), 4.43 (m, 2H, ³ J = 7.1 Hz, H _{W or k} .j, 4.41 (m, 2H, ³ J = 7.1 Hz, H _k - _{or k} ^» ), 3.83 (t, 8H, ³ J = 6.5 Hz, H _e 'e 1 -64 (quintet, 8H, ³ J = 5.3 Hz, Hr,r), 1.37 (m, 14H, Η ₉ · _{β τ} ), 1.25 (m, 16H, H _h ;hVf) _> 0 83 (m, 12H, H ). MS (ESI): m/z = 1898.4 [M ⁺ ] (calcd for m/z = 1898.6). Anal, calcd. for RUC107H108F12N7O8S2P: C, 62.87; H, 5.33; N, 4.80. Found: C, 62.93; H, 5.21 ; N, 4.64.

[Ru(18)(dcbpyH ₂ )(ppy-(CF ₃ )2)]PF6 (14)

A 3:1 :1 DMF/H ₂ 0/NEt ₃ mixture containing 19 (240 mg, 0.118 mmol) was heated at reflux for 18 h to produce a dark brown solution. After solvent removal in vacuo the resultant solid was purified by column chromatography [Sephadex;

Acetone] and isolated to afford 40 mg (62.7%) of a brown solid. MS (ESI): m/z = 1842.7 [M ⁺ ] (calcd for [RuC ₀ 3HiooF ₆ N ₇ OeS2] ⁺ : m/z = 1842.6). Anal, calcd. for

RuC ₁₀ 3HiooFi2N708S ₂ P: C, 62.23; H, 5.32; N, 5.00. Found: C, 62.75; H, 5.07; N, 4.93.

Physical Methods

D and 2D ¹ H and ³ C spectra were recorded at 400 MHz and 100 MHz, respectively, on a Bruker AV 400 instrument at ambient temperature unless otherwise stated. Electrochemical measurements were performed under anaerobic conditions with a Princeton Applied Research VersaStat 3 potentiostat using dry solvents, Pt working and counter electrodes, a Ag pseudoreference electrode, and 0.1 M NBu ₄ BF ₄ supporting electrolyte. Electronic spectroscopic data were collected on DMF solutions using a Cary 5000 UV-vis spectrophotometer (Varian). Steady-state emission spectra were obtained at room temperature using an Edinburgh Instruments FLS920

Spectrometer equipped with a Xe900 450W steady state xenon arc lamp, TMS300-X excitation monochromator, TMS300-M emission monochromator, Hamamatsu

R2658P PMT detector and corrected for detector response. Lifetime measurements were obtained at room temperature using an Edinburgh Instruments FLS920

Spectrometer equipped with Fianium SC400 Super Continuum White Light Source, Hamamatsu R3809U-50 Multi Channel Plate detector and data were analyzed with Edinbrugh Instruments F900 software. Curve fitting of the data was performed using a non-linear least squares procedure in the F900 software. Ceil Fabrication

Photoanodes were prefabricated by Dyesol, Inc. (Australia) with a screen- printable Ti0 ₂ pastes (18-NRT and WER4-0, Dyesol™). The active area of the Ti0 ₂ electrode is 0.28 cm ² with a thickness of 12 μηι (18-NRT) and 3 μνη (WER4-0) on fluorine-doped tin-oxide (FTO; TEC8 (8 Ω cm ^"2 )). T1O2 substrates were treated with TiCI ₄₍ aq) (0.05 M) at 70 °C for 30 min and subsequently rinsed with H ₂ 0 and dried prior to heating. The electrodes were heated to 450 °C for 20 min under ambient atmosphere and allowed to cool to 80 °C before dipping into the dye solution. The anode was soaked overnight for 16 h in an ABS EtOH solution containg dye (-0.25 mM) and chenodeoxycholic acid (-2.5 mM). The stained films were rinsed copiously with ABS EtOH and dried. The cells were fabricated using Pt-coated counter- electrode (FTO TEC-15 (15 Ω cm ^"2 )) and sealed with a 30 pm Surlyn (Dupont) gasket by resistive heating. An acetonitrile based electrolyte solution: (0.6M butylmethyl- imidazolium iodide, 0.06M l ₂ , 0.1 M sodium iodide, 0.1 M guanidinium thiocyanate and 0.5 terf-butylpyridine in acetonitrile) was introduced to the void via vacuum

backfilling through a hole in the counter electrode. The hole was sealed with an aluminum-backed Bynel foil (Dyesol™). After sealing, silver bus bars were added to all cells.

Dye Desorption Studies

Photoanodes containing dyes 10 and 14 were prepared according to the method described in the cell fabrication section. The dye soaked films were desorbed with 0.1 M NBu ₄ OH in ABS EtOH (10) or DMF (14). Calibration curves were constructed in the respective solvents and used to determine the amount of dye loading.

Cell Characterization

Photovoltaic measurements were recorded with a Newport Oriel solar simulator (Model 9225A1 ) equipped with a class A 150 W xenon light source powered by a Newport power supply (Model 69907). The light output (area = 5 cm χ 5 cm) was calibrated to AM 1 .5 using a Newport Oriel correction filter to reduce the spectral mismatch in the region of 350-700 nm to less than 1 .5%. The power output of the lamp was measured to 1 Sun (100 mW cm ^"2 ) using a certified Si reference cell. The current-voltage {l-V) characteristic of each cell was obtained by applying an external potential bias to the cell and measuring the generated photocurrent with a Keithley digital source meter (Model 2400). All cells were measured with a mask size of 0.28 cm ² or 0.13 cm ² . IPCE measurements were performed on a QEX7 Solar Cell Spectral Response Measurement System from PV Instruments, Inc. The system was calibrated with a photodiode that was calibrated against NIST standard I755 with transfer uncertainty less than 0.5% between 400-1000 nm and less than 1 % at all other wavelengths. All measurements were made in AC mode at 4 Hz chopping frequency under a bias light between 0.01 to 0.1 sun. The system was calibrated and operated in Beam Power mode. Electrochemical impedance spectroscopy (EIS) was measured on a Gamry EIS300 potentiostat. All EIS measurements were performed in the dark and scanned a frequency range from 100 kHz to 0.5 Hz with a 10mV voltage modulation applied to the bias.

Single crystal X-ray diffraction data

A dark purple, block shaped, crystal of [Ru(bpy)(deeb)(ppy)]PF ₆ was grown in a crystallization tube from a layered mixture of MeOH/Hexanes. The crystal was then coated with Paratone 8277 oil (Exxon) and mounted on a glass fiber. All

measurements were made on a Nonius KappaCCD diffractometer with graphite

47,48

monochromated Mo-Kc radiation. Details of crystal data, data collection and structure refinement are not shown. The data were corrected for Lorentz and polarization effects and for absorption using multi-scan methods. The structure was solved by the direct methods ⁴⁹ and expanded using Fourier techniques. ⁵⁰ The non- hydrogen atoms were refined anisotropically. The hydrogen atoms were included at geometrically idealized positions and were not refined. The final cycle of full-matrix least-squares refinement using SHELXL97 ⁵¹ converged with unweighted and weighted agreement factors, R = 0.0817 and wR = 0.1949 (all data), respectively, and goodness of fit, S = 1.049. The weighting scheme was based on counting statistics and the final difference map had no chemically significant features. The C33-C34 bond distance was fixed to match that of the analogous C36-C37 bond distance due to disorder in the ethyl pedant group in one of the ester moieties. Attempts to partition "PART" the PF ₆ had no influence on the agreement factors since more than two positions were made available due to disorder on the counter anion moiety of the molecule. The PLATON/SQUEEZE program ⁵² was employed to deal with disordered and partial occupancy MeOH/hexane molecules of solvation. RESULTS - EXAMPLE 3

Complex 14 was formed by the addition of the cyclometalating ligand to the metal prior to the synchronous addition of the two polypyridyl ligands. The TPA- functionalized chelating ligand 18 was furnished through a Suzuki cross-coupling reaction of 4,4 ^, -dibromo-2,2'-bipyridine with proligand 17 (Scheme of Figure 15). Addition of 18 and 4,4'-diethylester-2,2'-bipyridine (deeb) to [Ru(CH ₃ CN) ₄ (ppy- (CF ₃ ) ₂ )]PF ₆ (16) in an ABS EtOH/CHCI ₃ (3:1 ) solvent mixture yielded the ester derivative of 14, 19. 18 is soluble in CHCI3, but the formation of undesired byproducts is observed in this solvent thus lowering the overall reaction yields (-52.5 %). The constitution of 19 was established by ¹ H NMR spectroscopy, high-resolution mass spectrometry and elemental analysis. The deprotection of ester groups of 19 to produce 14 was achieved overnight in refluxing DMF/H ₂ 0/NEt3 (3:1 :1 ).

Dye 14 is insoluble in most polar organic solvents (e.g. MeOH, MeCN, DMSO) - even with the addition of NaOH - but is readily soluble in DMF. Dye 14 can be easily constituted in low-polarity organic solvents (e.g. CH2CI2, CHCI3, acetone, Et20), thus indicating that the solubility of the complex is dominated by 18. The ¹ H NMR spectrum of 14 in ds-DMF displayed broad, poorly resolved signals (not shown), which we attribute to slow molecular tumbling on the NMR timescale arising from the large size of the complex. Elevated temperatures (e.g., 373 K) yielded a nominal improvement in spectral resolution. Notwithstanding, ESI-MS and elemental analysis supported the identity of 14. The isomer shown in Figure 16 is based on the structural determination of a related complex, [Ru(bpy)(deeb)(ppy)]PF6 (the diethyl ester of compound 12; Figure 17). Note that this result provides the first structural confirmation of the absolute configuration of a //vs-heteroleptic Ru complex; namely, the Ru-C bond is positioned trans to the electron-deficient deeb.

The UV-vis spectrum of 14 (Figure 18) reveals a relatively intense band centred at 580 nm (3.3 x 10 ⁴ M ^"1 cm ^'1 ) ascribed to a "metal"-to-ligand charge transfer (MLCT) transition from the Ru-aryl fragment to the dcbpyH2 ligand. ¹⁸ The large intensity of the band centred at 465 nm (6.7 ^χ 10 ⁴ M ^"1 cm ^"1 ) arises from intraligand charge-transfer (ILCT) bands emanating from the TPA groups complementing the MLCT bands. ⁵³ Excitation of 14 at λ = 580 nm in degassed DMF generates an emission peak at λ = 797 nm with a lifetime of 46 ns.

The cyclic voltammogram (CV) of 14 recorded in DMF indicates a quasi- reversible oxidation process at +0.97 V vs NHE (Figure 18, inset). The large peak separation (Δ£ _ρ ~ 170 mV) is rooted in the nearly coincident Ru and TPA oxidation processes; e.g., the first oxidation potentials of 18 and 10 in DMF are observed at +0.96 V and +0.99 V, respectively (Figure 18, inset). The oxidation potential of 14 is not anticipated to deviate significantly from that of 10 because the HOMO is confined to the metal and the aryl ring. (Efforts to resolve the individual redox processes of 14 by square-wave voltammetry were not successful.) An irreversible or quasi-reversible TPA oxidation process superimposed with the ostensibly reversible Ru^/Ru" redox couple presumably causes the larger cathodic signal in the CV of 14. The quasi- reversible reductive wave at -1.17 V is assigned to the anchoring dcbpyH ₂ ligand of 14. The £ ₀ -o energy of 1.76 eV determined from the intersection of the absorption and emission curves corresponds to an £(S ⁺ /S*) of ca. -0.79 V (assuming the metal-based HOMO resides at +0.97 V), which is suitable for efficient electron injection into

Ti0 ₂ . ⁵ ' ⁵⁴

The absorption properties and ground- and excited-stated potentials of 14 were poised for sensitizing Ti0 ₂ in the DSSC. Cells were therefore constructed by immersing Ti0 ₂ photoelectrodes (12 pm active + 3 pm scattering layer) in absolute ethanol solutions of 14 with and without chenodeoxycholic acid (CDCA) present. Prior to sealing, the cells were filled with an electrolyte containing 0.6 M 1 -butyl-3- methylimidazolium iodide (BMII), 0.06 M l ₂ , 0.1 M Nal, 0.5 M 4-tertbutylpyridine and 0.1 M guanidinium thiocyanate. The photocurrent density-voltage diagrams for 14 are depicted in the inset of Figure 19 along with performance parameters listed in Table 4. The performance is effectively the same at full active area (Entries 5 and 6) with marginal differences observed in \Ζ ₀₀ (Δ = 0.01 V) and FF (Δ = 0.02). A more significant difference is evident with the J _sc (Δ= 1.1 mA/cm ² ). Overall the performances with and without coadsorbent are 5.9 and 6.2% respectively. The incident-photon-to- current-efficiency (IPCE) trace for 14 shows an onset of current at nearly 790 nm and the curve plateaus between 65 - 70 % in the region of 450-600 nm (Figure 19). A minimal enhancement is observed from 350-600 nm for devices without CDCA present, presumably a consequence of better dye loading in these devices (vide infra). One possible cause of the low IPCE values is a normalized diffusion length (L _n ) that was calculated to be less than the film thickness at V„c, both in the presence (0.6L _n ) and absence of coadsorbent (0.8L _n ). This condition would effectively reduce the charge collection efficiency, as well as V ₀ c and J _sc . Table 4 - Device characteristics for cells containing 10 and 14.

Entry Dye Active Area Coadsorbent ³ Voc/V Jsc mA cm ^"2 FF ? * (%)

(cm ² )

1 10 0.28 Yes 0.68 15.8 0.60 6.4

2 10 0.28 No 0.63 13.0 0.64 5.3

3 10 0.13 Yes 0.66 16.3 0.68 7.3

4 10 0.13 No 0.60 13.7 0.67 5.6

5 14 0.28 Yes 0.65 14.6 0.62 5.9

6 14 0.28 No 0.66 15.7 0.60 6.2

7 14 0.13 Yes 0.59 15.0 0.64 5.7

8 14 0.13 No 0.63 17.1 0.67 7.3 a Coadsorbent is chenodeoxycholic acid.

b Performance of DSSCs measured under AM1.5 light conditions at 1 sun intensity using 12 pm active + 3 μιτι scattering Τΐ0 ₂ layers. All cells were filled with an electrolyte consisting of 0.6 M 1-butyl-3-methylimidazolium iodide (BMII), 0.06 M I2, 0.1 M Nal, 0.5 M 4-tertbutylpyridine and 0.1 M guanidinium thiocyanate.

The larger photocurrent observed in the absence of CDCA is attributed to a higher dye loading on the surface of T1O2. This claim is supported by dye desorption studies indicating a surface concentration of 14 on Ti0 ₂ as 5.7 and 4.2 χ 10 ^"8 mol/cm ² in the absence and presence of the coabsorbent, respectively. Surprisingly, an opposite trend was observed for 10: a higher dye loading (8.1 χ 10 ^"8 mol/cm ² ) was found for substrates with CDCA compared to those without (5.4 χ 10 ^"8 mol/cm ² ). Despite these differences, the disparities in cell performance for 10 and 14 were nominal (Entries 1 and 5).

Further insight into the performance of DSSCs composed of 10 and 14 was obtained from electrochemical impedance spectroscopy (EIS) data (Figure 20), which was modelled with the transmission line (Figure 21 ). Figure 20(A) shows that the R _c i values of 14 are the same with and without the coabsorbent, while it is higher for 10 without CDCA. This result suggests that 10 is better than 14 at protecting the surface of Ti0 ₂ , presumably due to less space between the dyes and/or better packing between the hexyl chains closer to the surface. The transport resistance (/¾) is effectively the same with or without CDCA in devices sensitized by 14, but in the case of 10 it is higher without CDCA thereby offsetting the advantage of the increased R _cl (Figure 20(B)). L _n values are therefore approximately equivalent for devices sensitized by 10 and 14 that do not contain CDCA. The charge-transfer capacitance (C _ct ), which can be used as a metric for the electron concentration in Ti0 ₂ , is the only parameter to significantly differ (Figure 20(C)): the highest value was observed for 14 without CDCA (Entry 6). This result is consistent with the larger J _sc for the device containing 14 with coadsorbent (Entry 5) compared to that of 10 without CDCA (Entry 2).

DISCUSSION

The central aim of studies of Example 1 was to exploit the mixed-metal/ligand character of the HOMO for 1 by placing conjugated substituents on the anionic fragment of the bidentate C ^A N ligand while holding the balance of the structure at parity. By extending the HOMO and optical cross-section of the molecule, large ε values could be produced as a result of the increased charge separation distance in the excited state; thus, we furnished the 2-phenylpyridine ligand of Ru(dcpbyH ₂ ) ₂ (2- phenylpyridine) with aromatic substituents to form compounds 7-9. For the purposes of generating dyes for the DSSC where I7I ₃ ^' is used as the electrolyte, the HOMO energy level must be appropriately positioned to accommodate a sufficiently large driving force for dye regeneration. For this reason, electron-withdrawing substituents on the C ^A N ligand are desirable to avoid raising the energy of the HOMO level above that of the redox couple of the electrolyte; that is, E ₀ x > ~0.5 V versus NHE. This line of reasoning prompted us to study how the oxidation potential of 7 is affected when the phenyl substituent is replaced with the -4-pyridyl group of 8. Compound 9 was prepared in this same vein by utilizing an aldehyde to withdraw electron density from the metal; this compound also provides a platform for examining how the torsional strain between adjacent aromatic rings affects the optical properties.

The C ^A N ligands HL1-HL5, HL7-HL9 are all readily accessible through carbon- carbon cross-coupling procedures. The general synthetic protocol for isolating the target complexes was achieved using an initial cyclometalation step to form a cyclometalated intermediate(s) followed by coordination of the polypyridyl dcbpyH ₂ ligands. This strategy offers numerous advantages to the established method of synthesizing derivatives of 1. For instance, the more common approach of binding the C ^A N ligand to cis-Ru(dcbpyH ₂ )2Cl2 requires that the metal precursor be kept in the dark to avoid isomerization to the trans form. This route also generates homoleptic byproducts that ultimately lower the yields of reactions involving cis-Ru(dcbpyH ₂ ) ₂ CI ₂ . Not only are said obstacles overcome with the synthetic route described herein, but our protocol also provides a more efficient pathway for isolating Ru dyes containing a combination of bidentate polypyridyl and C ^A N ligands.

The electrochemical properties of the entire series exhibit an exquisite sensitivity to substituents on the C ^A N ligand. The reversibility of the oxidation wave indicates that the metal is the primary redox-active component; however, the E _ox values are particularly responsive to substituents on the phenyl ring arising from the direct interaction with the HOMO that is extended over the

ligand. The highest E _ox value is observed for 3 among the complexes containing a single -NO2 group because the substituent is situated para to the organometallic bond. The (quasi-) irreversibility of the first reduction waves for 2-5 is consistent with reduction of the -NO2 groups; however, the first reduction process for 3 may also involve the dcbpyH ₂ ligands. This possibility is supported by a quasireversible reduction wave, TD-DFT calculations and the observation of a weak emission signal for 3a. Our data also shows that a single -NO2 group increases the E _ox value more than the presence of two -F substituents.

Despite the observation that the LUMO is localized primarily to the -NO2 group(s), these compounds provide some promising insight in the context of chromophore design for light-harvesting applications; namely, the extension of the π- system of the C ^A N ligand clearly leads to a significant increase in ε values. This feature is reflected by broad absorption bands with ε values that can be 2-fold greater than that of 1. Compound 3, for instance, exhibits the most intense profile of the entire series. This observation emphasizes the importance of delocalizing the ground-state orbital character as a means of increasing the optical cross-section of the dye. On this basis, conjugated substituents were installed para to the Ru-C bond in pursuit of complexes with significantly higher intensity absorption bands relative to 1. The poor solubility of compounds 7-9 led to the preparation of deprotonated versions 7a-9a to extract accurate ε values. The intensity of the band centered at about 410 nm (i.e., max3) increases as the electron-withdrawing nature of the aromatic moiety increases. Consequently, 9a exhibits the most intense and broad absorption profile in the visible region of any protonated or deprotonated complex evaluated in this study.

Although 7a contains an additional aromatic ring relative to 1 , torsional strain between the two phenyl rings inhibits conjugation resulting in little improvement in the light-harvesting properties. The E _ox value is also slightly lower than that of 1a; thus, 8a was prepared as a means of increasing the oxidation potential. The installation of a thiophene group proved to be a viable strategy for enhancing conjugation on the basis that the spectral profile of 9a is more intense than that of 1a. The presence of the aldehyde at the 2-position of the thiophene also imposes electron-withdrawing character on the substituent, which is reflected by the higher E _ox value relative to 8a.

The -N0 ₂ compounds 2-5 are likely not ideal for sensitizing semiconducting material because the excited -states are, in large part, quenched by the strongly electron-withdrawing substituents. The aromatic susbstituents of 7a and 8a did not produce superior photophysical properties despite the extension of the π system owing to the steric encumbrance of the adjacent six-membered rings. Compound 9a appears to be a particularly promising candidate for the DSSC (where the anode is Ti0 ₂ and the electrolyte is I7I ₃ ^" ): the E _ox value is higher than that of 1a; the spectral profile is significantly more intense than that of 1a; and the orbital structure is poised for electron-injection and dye regeneration. Results from this study demonstrate that expansion of the HOMO is a valid strategy for producing compounds that may exceed the performance of benchmark complexes reported by Gratzel et al. (J Am. Chem. Soc. 2009, 131 , 5930-5934). ⁹

In the studies of Example 2, the inventors unexpectedly found that the addition of electron rich aromatic groups (e.g. 2-hexylthiophene) to the bpy ligand required that there be -CF ₃ groups present on the phenyl ring. The inclusion of the trifluoromethyl substituents was critical in order for the E _ox value of 10 to be compatible with dye regeneration by electrolytes containing I7I ₃ ^" . Other cyclometalated dyes that did not contain strong electron-withdrawing groups exhibited low power conversion efficiencies because regeneration was thermodynamically limited. Light absorption by 10 was not compromised by the use of strong-electron withdrawing groups and occurred beyond 700 nm. Performance with 10 exceeded that of standard dye 11 and also, unexpectedly, enabled the best power conversion efficiency (5.5%) for a device containing a Ru dye and cobalt-based electrolyte, at 1 Sun illumination, without the use of blocking layers.

It has been found through the experiments of Example 3 that the

cyclometalating ligand and TPA groups of 14 work together to produce a PCE of >7% in the DSSC. This high efficiency is made possible by the TPA groups acting as blocking layers between the semiconductor and electrolyte to overcome the inherently low dye-loading.

The device results for 14 are unique in that CDCA does not improve V _oc and/or Jsc- A similar observation for the organic dye D35 reported by Jiang et a/. ⁵⁵ was rationalized by a highly ordered dye arrangement on the surface limiting the uptake and effect of CDCA. This scenario could also be the case for 14, which is indirectly supported by the similarity in dye loading for D35 and 14. Regardless, the highest efficiency for 14 was observed in the case with the highest dye loading, which was achieved in the absence of CDCA. A PCE of 6.2% at full active area (0.28 cm ² ) and 7.3% with a reduced mask size (0.13 cm ² ) were recorded. Despite the lower surface coverage of 14 relative to that of 10, the cell performances of the two are remarkably similar.

D35

CONCLUSIONS

The electrochemical and photophysical properties of a series of cyclometalated Ru(ll) complexes related to 1 were examined to elucidate the effect of modifying the anionic fragment of the C ^A N ligand with conjugated substituents. It is shown that the installation of substituents para to the organometallic bond imparts the greatest influence on the redox behavior and optical properties. The electron-withdrawing character of the substituents are reflected by substantial changes in E _o values, a consequence of extending the HOMO beyond the phenyl ring of the C ^A N ligand. Expansion of the HOMO over the substituent is most effective in the case where torsional strain is reduced (i.e., 9a). In effect, this strategy produces a larger spectral envelope for 9a relative to 1a. The presence of an EWG on the thiophene also maintains a higher oxidation potential relative to 1a. These collective observations provide guiding principles that are critical to the evolution of cyclometatated Ru(ll) chromophores.

The inventors have thus discovered a high-efficiency trisheteroleptic cyclometalated Ru sensitizer. The efficacy of this NCS ^" - free dye is a consequence of a sufficiently high Ru /Ru redox potential achieved by installing electron-withdrawing groups at R ³ , thereby enhancing light absorption by placing thiophenes at R ² , and suppressing charge recombination with terminal alkyl groups on said thiophenes. A performance of 7.3% was achieved at AM1.5 and 8.3% at half that light intensity. The dye has also been demonstrated that a noncorrosive cobalt electrolyte achieves an efficiency of 5.5% and a photocurrent of 11.8 mA cm ^"2 under full sun illumination. These results provide an important breakthrough for making high-performance cyclometalated Ru dyes for use in the DSSC.

Example 3 provides a trichromic cyclometalated Ru dye that does not bear NCS ^" ligands. ^56,57 A power conversion efficiency (PCE) in excess of 7% in the dye- sensitized solar cell was observed despite having a large molecular footprint in Ti0 ₂ . This feature is significant in view of the apparent need for DSSC dyes to have a HOMO level positioned at ca. >0.9 V vs NHE to be regenerated by I ^" , ^27,58 which is consistent with the relevant redox couple for the electrolyte being defined by E°\ = 0.8+/-0.1 V vs NHE in MeCN. ⁵⁹ A particularly relevant example to this work is IJ-1 reported by Ko et al., which has two NCS ^" ligands and yields a PCE of 10.3%. ⁶⁰ The lower performance of 14 may be due to the lower driving force for intramolecular electron-transfer (i.e. reduction of the photo-oxidized Ru site by the TPA) relative to IJ-1 because the two NCS ^" groups do not raise the HOMO energy to the same extent as a ppy ^" ligand (although differences in cell fabrication cannot be excluded).

TABLE 1 : Electrochemical and electronic spectroscopy data for cyclometalated Ru(ll) compounds 1-5 and 7-9 from Example 1.

UV-vis data E _v2 (V vs NHE)

Compound maxi (nm) max2 (nm) max3 (nm) m (nm) £ox1 £red1 £(S+/S*)(V vs NHE)

[Ru(dcbpyH ₂ ) ₂ (L1)]PF ₆ (1) 575 503 413 827 - - -

[Ru(dcbpyH ₂ ) ₂ (L2)]PF ₆ (2) 554 (0.9) 491 (0.8) 405 (1.1 ) - +1.09 -0.96 -

[Ru(dcbpyH ₂ ) ₂ (L3)]PF ₆ (3) 545 (1.9) 494 (1.8) 405 (2.2) 794 + 1.12 -0.95 -0.67

[Ru(dcbpyH ₂ ) ₂ (L4)]PF ₆ (4) 557 (1.9) - 401 (1.7) - + 1.08 -0.94 -

[Ru(dcbpyH ₂ ) ₂ (L5)]PF ₆ (5) 532 (1.2) - 379 (1.2) - +1.21 -0.72 -

(Bu ₄ N) ₃ [Ru(dcbpy)(dcbpyH)(L1)]PF ₆ (1a) 563 (2.0) 496 (1.6) 409 (2.3) 810 +0.64 -1.47 -1.10

(Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L3)]PF ₆ (3a) 530 (2.0) - 393 (1.9) 781 +0.80 -1.12 -0.99

(Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L7)]PF ₆ (7a) 563 (1.6) 497 (1.3) 408 (1.8) 802 +0.61 -1.50 -1.12

(Bu ₄ N) ₃ [Ru(dcbpyH ₂ ) ₂ (L8)]PF ₆ (8a) 556 (1.6) 494 (1.4) 382 (2.4) 794 +0.65 -1.49 -1.12

(Bu ₄ N) ₃ [Ru(dcbpy) ₂ (L9)]PF _B (9a) 550 (1.7) 492 (2.2) 412 (2.8) 788 +0.68 -1.45 -1.08

UV-vis data were recorded in MeOH; the ε values are indicated in the UV-vis data columns in parentheses with units of ^χ 10 ⁴ M ¹ cm ^{- 1} ; the E1/2 data were collected using 0.1 M NBu ₄ BF ₄ DMF solutions at 200 mV/s and reference to a [Fc]/[Fc] ⁺ internal standard followed by conversion to NHE ([Fc]/[Fc] ⁺ vs NHE = 0.69 V); the E(S ⁺ /S*) data were calculated using E(S ⁺ /S*) = E(SVS) - E _(0-0 ) wherein Ε _(0- ο ₎ is obtained from the higher energy side of corrected emission band where the intensity is ca. 10% of the maximum;

References

(1 ) O'Regan, B.; Gratzel, M. Nature 1991 , 353, 737.

(2) Hagfeldt, A.; Boschloo, G.; Sun, L; Kloo, L; Pettersson, H. Chem. Rev. 2010, 110, 6595.

(3) Hagfeldt, A.; Boschloo, G.; Sun, L; Kloo, L; Pettersson, H. Chem. Rev.

2010, 110, 6595.

(4) Shi, D.; Pootrakulchote, N.; Li, R.; Guo, J.; Wang, Y.; Zakeeruddin, S. M.; Gratzel, M.; Wang, P. J. Phys. Chem. C 2008, 112, 17046.

(5) Ardo, S.; Meyer, G. J. Chem. Soc. Rev. 2009, 38, 115.

(6) Anderson, A. Y.; Barnes, P. R. F.; Durrant, J. R.; O'Regan, B. C. J.

Phys. Chem. C 2011 , 115, 2439.

(7) Boschloo, G.; Hagfeldt, A. Acc. Chem. Res. 2009, 42, 1819.

(8) Yu, Q.; Wang, Y.; Yi, Z.; Zu, N.; Zhang, J.; Zhang, M.; Wang, P. ACS Nano 2010, 4, 6032.

(9) Yella, A.; Lee, H.-W.; Tsao, H. N.; Yi, C; Chandiran, A. K.; Nazeeruddin,

M. K.; Diau, E. W.-G.; Yeh, C.-Y.; Zakeeruddin, S. M.; Gratzel, M. Science 2011 , 334, 629.

(10) Bessho, T.; Yoneda, E.; Yum, J.-H.; Guglielmi, M.; Tavernelli, I.; Imai, H.; Rothlisberger, U.; Nazeeruddin, M. K.; GraAatzel, M. J. Am. Chem. Soc. 2009, 131, 5930.

(1 1 ) Daeneke, T.; Kwon, T.-H.; Holmes, A. B.; Duffy, N. W.; Bach, U.;

Spiccia, L. Nat. Chem. 2011 , 3, 21 1.

(12) Bessho, T.; Zakeeruddin, S. M.; Yeh, C.-Y.; Diau, E. W.-G.; Gratzel, M. Angew. Chem., Int. Ed. 2010, 49, 6646.

(13) Hamann, T. W.; Jensen, R. A.; Martinson, A. B. F.; Van, R. H.; Hupp, J.

T. Energy Environ. Sci. 2008, 1, 66.

(14) Robertson, N. Angew. Chem. Int.Ed. 2006, 45.

(15) Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.; Miiller, E.; Liska, P.; Vlachopoulos, N.; Gratzel, M. J. Am. Chem. Soc. 1993, 115.

(16) Bomben, P. G.; Robson, K. C. D.; Sedach, P. A.; Berlinguette, C. P.

Inorg. Chem. 2009, 48, 9631.

(17) Bomben, P. G.; Koivisto, B. D.; Berlinguette, C. P. Inorg. Chem. 2010, 49, 4960.

(18) Bomben, P. G.; Robson, K. C. D.; Sedach, P. A.; Berlinguette, C. P. Inorg. Chem. 2009, 48, 9631.

(19) Bessho, T.; Yoneda, E.; Yum, J.-H.; Guglielmi, M.; Tavernelli, I.; Imai, H.; Rothlisberger, U.; Nazeeruddin, M. K.; Gratzel, M. J. Am. Chem. Soc. 2009, 131, 5930.

(20) Fabregat-Santiago, F.; Bisquert, J.; Garcia-Belmonte, G.; Boschloo, G.; Hagfeldt, A. Sol. Energy Mater. Sol. Cells 2005, 87, 1 17.

(21 ) Palmer, M. J.; Kenny, J. A.; Walsgrove, T.; Kawamoto, A. M.; Wills, M. J. Chem. Soc, Perkin Trans. 1 2002, 416.

(22) Hoertz, P. G.; Staniszewski, A.; Marton, A.; Higgins, G. T.; Incarvito, C. D.; Rheingold, A. L; Meyer, G. J. J. Am. Chem. Soc. 2006, 128, 8234.

(23) Staats, H.; Eggers, F.; Hass, O.; Fahrenkrug, F.; Matthey, J.; Luening,

U.; Luetzen, A. Eur. J. Org. Chem. 2009, 4777.

(24) Brusso, J. L.; Hirst, O. D.; Dadvand, A.; Ganesan, S.; Cicoira, F.;

Robertson, C. M.; Oakley, R. T.; Rosei, F.; Perepichka, D. F. Chem. Mater. 2008, 20, 2484.

(25) Zhou, Q.; Fitzgerald, K.; Boyle, P. D.; Henderson, W. A. Chem. Mater.,

22, 1203. (26) Feldt, S. M.; Gibson, E. A.; Gabrielsson, E.; Sun, L; Boschloo, G.;

Hagfeldt, A. J. Am. Chem. Soc, 132, 16714.

(27) Bomben, P. G.; Theriault, K. D.; Berlinguette, C. P. Eur. J. Inorg. Chem. 2011 , 1806.

(28) Gao, F.; Wang, Y.; Shi, D.; Zhang, J.; Wang, M.; Jing, X.; Humphry-

Baker, R.; Wang, P.; Zakeeruddin, S. M.; Gratzel, M. J. Am. Chem. Soc. 2008, 130, 10720.

(29) M.J. Frisch, G. W. T., H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T.A. Keith, G.A. Petersson, J.A. Montgomery, K.

Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J.

Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J.A. Pople. Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford, CT, EUA.

(30) Becke, A. D. Phys. Rev. A: Gen. Phys. 1988, 38, 3098.

(31 ) Becke, A. D. J. Chem. Phys. 1993, 98, 1372.

(32) Lee, C; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter 1988, 37,

785.

(33) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270.

(34) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.

(35) Rassolov, V. A.; Ratner, M. A.; Pople, J. A.; Redfern, P. C; Curtiss, L. A. J. Comput. Chem. 2001, 22, 976.

(36) Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327.

(37) Hirata, N.; Lagref, J. J.; Palomares, E. J.; Durrant, J. R.; Nazeeruddin,

M. K.; Gratzel, M.; Di Censo, D. Chem. Eur. J. 2004, 10, 595.

(38) Feldt, S. M.; Gibson, E. A.; Gabrielsson, E.; Sun, L.; Boschloo, G.;

Hagfeldt, A. J. Am. Chem. Soc. 2010, 132, 16714.

(39) Zhou, D.; Yu, Q.; Cai, N.; Bai, Y.; Wang, Y.; Wang, P. Energy &

Environmental Science 20 1 , 4, 2030.

(40) Tsao, H. N.; Yi, C; Moehl, T.; Yum, J.-H.; Zakeeruddin, S. M.;

Nazeeruddin, M. K.; Gratzel, M. ChemSusChem 2010, 4, 591.

(41 ) Nusbaumer, H.; Zakeeruddin, S. M.; Moser, J.-E.; Gratzel, M. Chem. Eur. J. 2003, 9, 3756.

(42) Klahr, B. M.; Hamann, T. W. Journal of Physical Chemistry C 2009, 113,

14040.

(43) Ondersma, J. W.; Hamann, T. W. Journal of Physical Chemistry C 2010, 114, 638.

(44) Nelson, J. J.; Amick, T. J.; Elliott, C. M. Journal of Physical Chemistry C 2008, 112, 18255.

(45) Yum, J. H.; Hagberg, D. P.; Moon, S. J.; Karlsson, K. M.; Marinado, T.; Sun, L. C; Hagfeldt, A.; Nazeeruddin, M. K.; Gratzel, M. Angew. Chem., Int. Ed. 2009, 48, 1576.

(46) Bomben, P. G.; Gordon, T. J.; Schott, E.; Berlinguette, C. P. Angew. Chem., Int. Ed. 2011 , 50, 10464.

(47) Otwinowski, Z.; Minor, W., Methods in Enzymology, Macromolecular Crystallography, Carter Jr., C. W.; Sweet, R. M. Eds., Academic Press 1997, 276A, 307.

(48) Hooft, R., COLLECT: Users Manual, Nonius B.V., Delft. The

Netherlands 1998. (49) Altomore, A.; Cascarano, M.; Giacovazzo, C; Guagliardi, A. J. Appl. Cryst. 1993, 26, 343.

(50) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; de Gelder, R.; Israel, R.; Smits, J. M. M., The DIRDIF-94 program system, Technical report of the Crystallography Laboratory, University of Nijmegen, The Netherlands 1994.

(51 ) Sheldrick, G. M. Acta Cryst. 2008, A64, 112.

(52) Spek, A. L., PLATON/SQUEEZE - A Multipurpose Crystallographic Tool, Utrecht University 2000.

(53) Robson, K. C. D.; Koivisto, B. D.; Yella, A.; Sporinova, B.; Nazeeruddin,

M. K.; Baumgartner, T.; Gratzel, M.; Berlinguette, C. P. Inorg. Chem. 2011 , 50, 5494.

(54) Listorti, A.; O'Regan, B.; Durrant, J. R. Chemistry of Materials 2011 , 23,

3381.

(55) Jiang, X.; Marinado, T.; Gabrielsson, E.; Hagberg, D. P.; Sun, L.;

Hagfeldt, A. J. Phys. Chem. C 2010, 114, 2799.

(56) Handa, S.; Wietasch, H.; Thelakkat, M.; Durrant, J. R.; Haque, S. A. Chem. Commun. 2007, 1725.

(57) Bonhote, P.; Moser, J.-E.; Humphry-Baker, R.; Vlachopoulos, N.;

Zakeeruddin, S. M.; Walder, L.; Gratzel, M. J. Am. Chem. Soc. 1999, 121, 1324.

(58) Bomben, P. G.; Robson, K. C. D.; Berlinguette, C. P. Coord. Chem. Rev.

2012, ASAP.

(59) Boschloo, G.; Gibson, E. A.; Hagfeldt, A. The Journal of Physical Chemistry Letters 2011 , 2, 3016.

(60) Yum, J.-H.; Jung, I.; Baik, C; Ko, J.; Nazeeruddin, M. K.; Gratzel, M. Energy Environ. Sci. 2009, 2, 100.