STATEMENT OF US GOVERNMENT SUPPORT

[0001] This invention was made with government support under Grant Nos. DE- SC0020008 and DE-SC0016526, awarded by the Department of Energy. The government has certain rights in the invention.

BACKGROUND

[0002] Metallopolymers have the potential to be next-generation materials for the energy sector, information storage, and materials synthesis. Uniquely, transition metal chemistry marries polymer science in these hybrid materials wherein the metal imparts new properties unimaginable for organic polymers alone. There is a need for new strategies to construct well-defined and rationally-designed metallopolymers with complete understanding of their optoelectronic and redox properties are necessary if their full potential is to be realized.

SUMMARY

[0003] Provided herein are metallopolymers comprising a plurality of monomer units, each monomer unit comprising: (a) a first transition metal; (b) a first 1,2,3-triazole substituted at one or more of the 1, 4, and 5 positions and the first 1,2,3-triazole conjugated directly or indirectly to the first transition metal; and (c) a first N-heterocyclic carbene (NHC) coordinated to the first transition metal.

[0004] Also provided herein are methods of preparing a metallopolymer according to any one of claims 1-33, comprising: admixing an azide-containing compound and an alkyne- containing compound to form the metallopolymer according to any one of claims 1-33, wherein one or both of the azide-containing compound and the alkyne-containing compound further comprises a transition metal and one or both of the azide-containing compound and the alkyne-containing compound further comprises an N-heterocyclic carbene.

[0005] Also provided herein are metallopolymers having a structure of formula (Ilia) or (Nib): (lllb) wherein: the dashed lines indicate optional double bonds; each L ³ is independently selected from a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six-membered monocyclic group having 1 to 3 ring heteroatoms selected from O, N, or S; each R ⁷ is independently selected from H, C1-10alkyl, C5-C8cycloalkyl, and Ar ³ , or both R ⁷ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; each R ⁸ is independently selected from H, C1- 10alkyl, C5-C8cycloalkyl, and Ar ³ , or both R ⁸ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, or 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; each R ⁹ is independently selected from H, C1-10alkyl, C5-C8cycloalkyl, and Ar ³ , or both R ⁹ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, or 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; n is 10 or more; m" is 1, 2, 3, or 4; M is a transition metal; and each Ar ³ is independently selected from C6-C22 aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. [0006] Also provided herein are methods of preparing a metallopolymer according to any one of claims 42-54, comprising: admixing an azide-containing compound and an alkyne- containing compound to form the metallopolymer according to any one of claims 42-54, wherein one or both of the azide-containing compound and alkyne-containing compound further comprise a transition metal. DETAILED DESCRIPTION [0007] Provided herein are metallopolymers having a structure represented by formula (I), (IIa), (IIb), (IIIa), (IIIb), (IV), (V), (VI), and/or (VII), and methods of making the metallopolymers of the disclosure. [0008] Modifications and other embodiments will come to mind to one skilled in the art to which the disclosed compounds and methods pertain to having the benefit of the teachings presented herein. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. [0009] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” can include the aspect of “consisting of.” Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0010] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

METALLOPOLYMERS

[0011] The disclosure provides metallopolymers comprising a plurality of monomer units, wherein each monomer unit comprises (a) a first transition metal; (b) a first 1,2,3-triazole substituted at one or more of the 1, 4, and 5 positions and the first 1,2,3-triazole is conjugated directly or indirectly to the first transition metal; and, (c) a first N-heterocyclic carbene (NHC) coordinated to the first transition metal. The 1 ,4,5 positions and the 1 ,2,3 positions of the triazole are determined based on International Union of Pure and Applied Chemistry (lUPAC) nomenclature at the date of filing, well-known by one of ordinary skill in the art.

[0012] The term “Click reaction” refers to a class of reactions well known to one of ordinary skill in the art, one example of which is a reaction between an azide and an alkyne to form a 1,2,3-triazole. In general, the metallopolymers of the disclosure can be prepared by an inorganic “Click” reaction, referred to herein as an “iCIick reaction.” The “iCIick reaction” of the disclosure refers to a1,3-dipolar cycloaddition involving one or more metals. The 1,3-dipolar cycloaddition combines an azide complex and an alkyne complex to form a 1 ,2,3-triazole, wherein the azide complex and/or the alkyne complex is coordinated to one or more metal-ions, resulting in the formation of a metallopolymer of the disclosure. In embodiments, the metallopolymers of the disclosure can include a 1,4,5-substituted 1,2,3- triazole resulting from an iCIick reaction. In embodiments, the iCIick reaction can result in a 1 ,5-substituted 1,2,3-triazole, or a 1,4-substituted 1,2,3-triazole. The selectivity towards 1,4- or 1,5-addition depends upon the metal or ions and other substituents on the acetylide, in addition to whether the reaction employs copper(l) as a catalyst.

[0013] Over the past few decades intense focus has centered on the preparation of organic polymers of various properties using the “organic” azide-alkyne cycloaddition reaction, without a metal atom. Breaking this mold and approach, metallopolymers via iCIick were successfully synthesized for the first time (Veige et al., Chem. Commun. 2017, 53, 9934-9937; Veige et al., Cu-catalyzed azide-Pt-acetylide cycloaddition: progress towards a conjugated metallopolymer via iCIick. Organometallics 2018, in revision) using PR ₃ substituted Pt(II) complexes. However, the conjugation length and light emission properties of these early metallopolymers were somewhat lackluster. In embodiments, the metallopolymers of the disclosure advantageously include N-heterocyclic carbene (NHC) ligands instead of PR3 ligands. It was found that the strong σ-donating capacity of NHC ligands bound to Pt(II) can advantageously elevate the platinum-centered d-d states to higher energy, reducing the probability of thermal activation which leads to quenching or suppression of the emission efficiency. Additionally, Pt(II) advantageously can adopt a square planar geometry, allowing Pt(II) complexes to exhibit higher energy d-d states relative to similar octahedral complexes such as iridium(III). As a consequence, Pt(II)-NHC complexes can exhibit interesting luminescence properties. For example, substituting PBu3 ligands in Pt(II) complexes for NHC ligands can result in a NHC-Pt-acetylide complex that has decidedly improved photophysical properties, relative to the complex including the PBu3 ligands. Square planar Pt(II)-NHC complexes can have cis or trans configurations. Previous reports detail the photophysical properties of cis-Pt(II)-NHC complexes featuring bidentate and tridentate cyclometalating ligands that tune their photophysical and electronic properties (Fuertes et al., Inorg. Chem.2017, 56, 4829-4839; Ko et al., Dalton Trans.2015, 44, 8433- 8443). Under-studied however, are the trans-NHC isomers (Juvenal et al., ACS Omega 2017, 2, 7433-7443; Winkel et al., Dalton Trans.2014, 43, 17712-17720). Part of the disclosure herein takes advantage of the high quantum efficiencies of Pt(II)-NHC luminescence by incorporating them into iClick metallopolymers as trans-stereoisomers. [0014] The first transition metal can generally be any transition metal, i.e., as found in groups 3 to 12 of the periodic table. In embodiments, the first transition metal is selected from the group of: Au, Pt, Rh, Pd, Ni, Ru, Co, Fe, Ir, W, Re, and Ag. In embodiments, the first transition metal is Pt, Rh, Pd, or Ni. In embodiments, the first transition metal is Pt. In embodiments, the first transition metal is Rh. [0015] In embodiments, each monomer unit of the metallopolymer of the disclosure can further include a second transition metal. In embodiments, the second transition metal is selected from the group of: Au, Pt, Rh, Pd, Ni, Ru, Co, Fe, Ir, W, Re, and Ag. In embodiments, the second transition metal is Pt, Rh, Pd, or Ni. In embodiments, the second transition metal is Pt. In embodiments, the second transition metal is Rh. In embodiments, the first transition metal and the second transition metal are the same transition metal. In embodiments, the first transition metal and the second transition metal are the same transition metal in the same oxidation state. In embodiments, the first transition metal and the second transition metal are the same transition metal, and, the first transition metal has a different oxidation state than the second transition metal. In embodiments, the first transition metal and the second transition metal are different transition metals. In embodiments, the first transition metal and the second transition metal are different transition metals in the same oxidation state. In embodiments, the first transition metal and the second transition metal are different transition metals, and, the first transition metal has a different oxidation state than the second transition metal. [0016] In general, each monomer unit includes a first 1,2,3-triazole substituted at one or more of the 1, 4, and 5 positions and the first 1,2,3-triazole is conjugated directly or indirectly to the first transition metal. As used herein, the term “conjugated directly or indirectly” refers to (i) a 1,2,3-triazole bonded directly to the first transition metal (i.e., conjugated directly), or (ii) a 1,2,3-triazole is bonded to an organic linker that is in turn bonded to the metal (i.e., conjugated indirectly). The organic linker, when present, is not necessarily limited and can be determined to be suitable by one of ordinary skill in the art. For example, the organic linker can be a C2 alkynyl, or a C2alkynyl-Ph. In embodiments, the first 1,2,3-triazole is conjugated directly to the first transition metal. In embodiments, the first 1,2,3-triazole is conjugated indirectly to the first transition metal. [0017] In embodiments, each monomer unit further comprises a second 1,2,3-triazole conjugated directly or indirectly to the first transition metal or the second transition metal. In embodiments, the second 1,2,3-triazole is conjugated directly to the first transition metal. In embodiments, the second 1,2,3-triazole is conjugated indirectly to the first transition metal. In embodiments, the second 1,2,3-triazole is conjugated directly to the second transition metal. In embodiments, the second 1,2,3-triazole is conjugated indirectly to the second transition metal. In embodiments, the second 1,2,3-triazole is substituted at one or more of the 1, 4, and 5 positions. [0018] In general, the first N-heterocyclic carbene coordinated to the first transition metal is not necessarily limited. As described above, the NHC can affect the energy level of the metal-centered d-d states, which in turn can affect the luminescence properties of the complex. Accordingly, the NHC can be selected to provide a metallopolymer having a desired luminescence property. N-heterocyclic carbenes have not been used before in metallopolymers. In embodiments, each monomer unit further comprises a second NHC coordinated to the first transition metal. [0019] In embodiments wherein each monomer unit comprises a second transition metal, the second transition metal can have at least one N-heterocyclic carbene coordinated to it. In embodiments, the second transition metal has two N-heterocyclic carbenes coordinated to it. [0020] In embodiments, each N-heterocyclic carbene of the disclosure can be independently selected from the group of: wherein, each R group is independently selected from the group of: H, C1-C20 alkyl, C4-C15 cycloalkyl, C2-C20 alkenyl, C6-C20 aryl, C1-C20 alkoxy, and C6-C20 aryloxy. In embodiments, at least one NHC is , wherein each R is independently H or C _1- 5alkyl. In embodiments, each NHC is , wherein each R is independently H or C1-5alkyl. In embodiments, each NHC is wherein each R is independently H or C1- ₅ alkyl. In embodiments, at least one NHC is , wherein each R is independently H or C1-5alkyl. In embodiments, each NHC is , , wherein Bu refers to n-butyl. In embodiments, each NHC is , wherein Cy refers to cyclohexyl. [0021] In general, n can be 3 or more. In embodiments, n can be 3 to 1,000,000, 10 to 1,00,000, 10 to 100,000, or 10 to 10,000, or 10 to 1000, 3 to 100, or 3 to 50, or 3 to 10. [0022] As used herein, the term “alkyl” refers to straight chained and branched saturated hydrocarbon groups containing one to thirty carbon atoms, for example, one to twenty two carbon atoms, or one to twenty carbon atoms, or one to ten carbon atoms. The term Cn means the alkyl group has “n” carbon atoms. For example, C4 alkyl refers to an alkyl group that has 4 carbon atoms. C1-22alkyl and C1-C22 alkyl refer to an alkyl group having a number of carbon atoms encompassing the entire range (i.e., 1 to 22 carbon atoms), as well as all subgroups (e.g., 1-20, 2-15, 1-10, 5-12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, and 22 carbon atoms). Nonlimiting examples of alkyl groups include, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl (1,1-dimethylethyl), 3,3- dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. [0023] As used herein, the term “cycloalkyl” refers to an aliphatic cyclic hydrocarbon group containing four to twenty carbon atoms, for example, four to fifteen carbon atoms, or four to ten carbon atoms (e.g., 4, 5, 6, 7, 8, 10, 12, 14, 15, 16, 17, 18, 19 or 20 carbon atoms). The term Cn means the cycloalkyl group has “n” carbon atoms. For example, C5 cycloalkyl refers to a cycloalkyl group that has 5 carbon atoms in the ring. C5-8 cycloalkyl and C5-C8 cycloalkyl refer to cycloalkyl groups having a number of carbon atoms encompassing the entire range (i.e., 5 to 8 carbon atoms), as well as all subgroups (e.g., 5- 6, 6-8, 7-8, 5-7, 5, 6, 7, and 8 carbon atoms). Nonlimiting examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Unless otherwise indicated, a cycloalkyl group can be an unsubstituted cycloalkyl group or a substituted cycloalkyl group. The cycloalkyl groups described herein can be isolated or fused to another cycloalkyl group, a heterocycloalkyl group, an aryl group and/or a heteroaryl group. [0024] As used herein, the term “alkenyl” is defined identically as “alkyl,” except for containing at least one carbon-carbon double bond, and having two to twenty carbon atoms, for example, two to twenty carbon atoms, or two to ten carbon atoms. The term Cn means the alkenyl group has “n” carbon atoms. For example, C4 alkenyl refers to an alkenyl group that has 4 carbon atoms. C2-7 alkenyl and C2-C7 alkenyl refer to an alkenyl group having a number of carbon atoms encompassing the entire range (i.e., 2 to 7 carbon atoms), as well as all subgroups (e.g., 2-6, 2-5, 3-6, 2, 3, 4, 5, 6, and 7 carbon atoms). Specifically contemplated alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, and butenyl. Unless otherwise indicated, an alkenyl group can be an unsubstituted alkenyl group or a substituted alkenyl group. [0025] As used herein, the term “alkynyl” is defined identically as “alkyl,” except for containing at least one carbon-carbon triple bond, and having two to twenty carbon atoms, for example, two to twenty carbon atoms, or two to ten carbon atoms. The term C _n means the alkynyl group has “n” carbon atoms. For example, C ₄ alkynyl refers to an alkynyl group that has 4 carbon atoms. C ₂ - ₇ alkynyl and C ₂ -C ₇ alkynyl refer to an alkynyl group having a number of carbon atoms encompassing the entire range (i.e., 2 to 7 carbon atoms), as well as all subgroups (e.g., 2-6, 2-5, 3-6, 2, 3, 4, 5, 6, and 7 carbon atoms). Specifically contemplated alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, and butynyl. Unless otherwise indicated, an alkenyl group can be an unsubstituted alkynyl group or a substituted alkynyl group. [0026] As used herein, the term “aryl” refers to monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) carbocyclic aromatic ring systems having six to twenty carbon atoms, for example six to fifteen carbon atoms or six to ten carbon atoms. The term C _n means the aryl group has “n” carbon atoms. For example, C ₆ aryl refers to an aryl group that has 6 carbon atoms in the ring. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unless otherwise indicated, an aryl group can be an unsubstituted aryl group or a substituted aryl group.

[0027] As used herein, the term “alkoxy” or “alkoxyl” refers to a “-O-alkyl” group. As used herein, the term “aryloxy” or “aryloxyl” refers to a “-O-aryl” group. As used herein, the term “heteroaryloxy” or “heteroaryloxyl” refers to a “-O-heteroaryl” group.

[0028] As used herein, the term “ether” refers to a “-R-0-R-” group, wherein each R independently is an alkyl, cycloalkyl, or aryl group. As used herein, the term “thioether” refers to a “-R-S-R-” group, wherein each R independently is an alkyl, cycloalkyl, or aryl group.

[0029] As used herein, the term “substituted," when used to modify a chemical functional group, refers to the replacement of at least one hydrogen radical on the functional group with a substituent. Substituents can include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, heterocycloalkyl, heterocycloalkenyl, ether, polyether, thioether, polythioether, aryl, heteroaryl, hydroxyl, oxy, alkoxy, heteroalkoxy, aryloxy, heteroaryloxy, ester, thioester, carboxy, cyano, nitro, amino, amido, acetamide, and halo (e.g., fluoro, chloro, bromo, or iodo). When a chemical functional group includes more than one substituent, the substituents can be bound to the same carbon atom or to two or more different carbon atoms.

[0030] As used herein, the term “heteroalkyl” is defined similarly as alkyl except that the straight chained and branched saturated hydrocarbon group contains, in the alkyl chain, one to five heteroatoms independently selected from oxygen (O), nitrogen (N), and sulfur (S). In particular, the term “heteroalkyl” refers to a saturated hydrocarbon containing one to twenty carbon atoms and one to five heteroatoms. In general, in embodiments wherein the heteroalkyl is provided as a substituent, the heteroalkyl is bound through a carbon atom, e.g., a heteroalkyl is distinct from an alkoxy or amino group.

[0031] As used herein, the term “heterocycloalkyl” is defined similarly as cycloalkyl, except the ring contains one to five heteroatoms independently selected from oxygen, nitrogen, and sulfur. In particular, the term “heterocycloalkyl” refers to a ring containing a total of five to twenty atoms, for example three to fifteen atoms, or three to ten atoms, of which 1, 2, 3, 4, or 5 of those atoms are heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur, and the remaining atoms in the ring are carbon atoms. Nonlimiting examples of heterocycloalkyl groups include piperdine, tetrahydrofuran, tetrahydropyran, dihydrofuran, morpholine, and the like. The heterocycloalkyl groups described herein can be isolated or fused to another heterocycloalkyl group, a cycloalkyl group, an aryl group, and/or a heteroaryl group. In some embodiments, the heterocycloalkyl groups described herein comprise one oxygen ring atom (e.g., oxiranyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl). [0032] As used herein, the term “heteroaryl” refers to a cyclic aromatic ring system having five to twenty total ring atoms (e.g., a monocyclic aromatic ring with 5-6 total ring atoms), of which 1, 2, 3, 4, or 5 of those atoms are heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur, and the remaining atoms in the ring are carbon atoms. Unless otherwise indicated, a heteroaryl group can be unsubstituted or substituted with one or more, and in particular one to four, substituents selected from, for example, halo, alkyl, alkenyl, OCF3, NO2, CN, NC, OH, alkoxy, amino, CO2H, CO2alkyl, aryl, and heteroaryl. In some cases, the heteroaryl group is substituted with one or more of alkyl and alkoxy groups. Heteroaryl groups can be isolated (e.g., pyridyl) or fused to another heteroaryl group (e.g., purinyl), a cycloalkyl group (e.g., tetrahydroquinolinyl), a heterocycloalkyl group (e.g., dihydronaphthyridinyl), and/or an aryl group (e.g., benzothiazolyl and quinolyl). Examples of heteroaryl groups include, but are not limited to, thienyl, furyl, pyridyl, pyrrolyl, oxazolyl, quinolyl, thiophenyl, isoquinolyl, indolyl, triazinyl, triazolyl, isothiazolyl, isoxazolyl, imidazolyl, benzothiazolyl, pyrazinyl, pyrimidinyl, thiazolyl, and thiadiazolyl. When a heteroaryl group is fused to another heteroaryl group, then each ring can contain five to twenty total ring atoms and one to five heteroatoms in its aromatic ring. [0033] As used herein, the term “hydroxy” or “hydroxyl” refers to the “-OH” group. As used herein, the term “thiol” refers to the “-SH” group. [0034] As used herein, the term “alkylthio” refers to a “-S-alkyl” group. As used herein, the term “arylthio” refers to a “-S-aryl” group. As used herein, the term “heteroarylthio” refers to a “-S-heteroaryl” group. [0035] As used herein, the term "halo" is defined as fluoro, chloro, bromo, and iodo. The term “haloalkyl” refers to an alkyl group that is substituted with at least one halogen, and includes perhalogenated alkyl (i.e., all hydrogen atoms substituted with halogen), for example, CH ₃ CHCl ₂ , CH ₂ ICHBr ₂ CH ₃ , or CF ₃ . [0036] Also provided herein are metallopolymers according to the foregoing disclosure having a structure of formula (I): wherein: NHC is an N-heterocyclic carbene; R ¹ is either a bond or selected from C _1-10 alkyl, C _2-6 alkynyl, C _0-3 alkynyl-C _3-6 cycloalkyl, C _0-3 alkynyl-Ar ¹ ; R ² is selected from a bond, an electron deficient species, and an electron rich species; R ³ is selected from C _1-10 alkyl, C _2-6 alkynyl, C _0-3 alkynyl-C _3-6 cycloalkyl, C _0-3 alkynyl-Ar ¹ , 1,2,3-triazole, C _1-10 alkyl-1,2,3-triazole, C _2-6 alkynyl-1,2,3-triazole, C _0-3 alkynyl-C _3-6 cycloalkyl- 1,2,3-triazole, and C _0-3 alkynyl-Ar ¹ -1,2,3-triazole; each L ¹ is independently selected from an N-heterocyclic carbene, a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six-membered cyclic group having 1 to 3 ring heteroatoms selected from O, N, and S; n is 10 or more; m is 1, 2, or 3; M is a transition metal; and each Ar ¹ is independently selected from C6-C22aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. [0037] As used herein, the term “cyclic group” refers to any ring structure comprising a cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or a combination thereof. A monocyclic group is a cyclic group comprising just one ring. The cyclic group can be referred to by the number of atoms in the ring back bone, for example, a “5-member cyclic group” refers to a cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or a combination thereof, wherein the cyclic group includes 5 atoms in the ring backbone. Unless otherwise indicated, a cyclic group can be an unsubstituted or a substituted cyclic group. [0038] In general, R ¹ can be either a bond or selected from C1-10alkyl, C2-6alkynyl, C0- 3alkynyl-C3-6cycloalkyl, C0-3alkynyl-Ar ¹ . In embodiments, R ¹ is selected from a bond, C1-5alkyl, C2-4alkynyl, and C2-3alkynyl-Ar ¹ . In embodiments, R ¹ is a bond. In embodiments, R ¹ is C2alkynyl. In embodiments, R ¹ is C2alkynyl-Ar ¹ . In embodiments, R ¹ is C2alkynyl-Ar ¹ , wherein Ar ¹ is Ph. [0039] In general, R ² can be selected from a bond, an electron deficient species, and an electron rich species. In embodiments, R ² is a bond. In embodiments, R ² is an electron deficient species. In embodiments, R ² is an electron rich species. [0040] As used herein, the term “electron rich species” refers to a chemical functional group or entity that can readily donate electrons/electron density to another functional group or entity, such as to an electron deficient species. The electron rich species used herein are not particularly limited and can be any electron rich species suitable for organic electronics, e.g., p-dopable polymers.. For example, the electron rich species can include, but are not limited to, functional groups selected from alkyl, cycloalkyl, organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, amines, amine oxides, amides, thiols, thioethers, various phosphate esters, amides, or the like.. In embodiments, the electron rich species includes an alkyl, a thioether, an ether, or an amine. In embodiments, the electron rich species is a heteroaromatic compound, such as thiophene or ethylenendioxythiophene, or the like. In embodiments, the electron rich species is selected from , , a d , wherein C8H17 and C6H13 refer to the linear isomer. [0041] As used herein, the term “electron deficient species” refers to a chemical functional group or entity that accepts electrons/electron density from another functional group or entity, such as from an electron rich species. The electron deficient acceptors used herein are not particularly limited and can be any electron deficient species suitable for organic electronics,e.g., n-dopable polymers.. For example, the electron deficient species can include, but are not limited to, functional groups selected from nitrates, nitrites, aryls, heteroaryls, sulfonyl, cyano, haloalkyl, ammonium, or the like. In embodiments, the electron deficient species is a heteroaromatic compound, e.g., pyridyl, benzothiadiazole, or the like. In embodiments, the electron deficient species includes a haloalkyl, a heteroaryl, or a s lf l f ti l I b di t th lectron deficient species is selected from [0042] In general, R ³ can be selected from C _1-10 alkyl, C _2-6 alkynyl, C _0-3 alkynyl-C _{3- 6} cycloalkyl, C _0-3 alkynyl-Ar ¹ , 1,2,3-triazole, C _1-10 alkyl-1,2,3-triazole, C _2-6 alkynyl-1,2,3-triazole, C0-3alkynyl-C3-6cycloalkyl-1,2,3-triazole, and C0-3alkynyl-Ar ¹ -1,2,3-triazole. In embodiments, R ³ is C1-5alkyl, C2-4alkynyl, C2-3alkynyl-Ar ¹ , 1,2,3-triazole, C2-4alkynyl-1,2,3-triazole, or C0- 3alkynyl-Ar ¹ -1,2,3-triazole. In embodiments, R ³ is C2alkynyl. In embodiments, R ³ is C2alkynyl- Ar ¹ . In embodiments, R ³ is C2alkynyl-1,2,3-triazole. In embodiments, R ³ is 1,2,3-triazole. In embodiments, R ³ is C0alkynyl-Ar ¹ -1,2,3-triazole. In embodiments, R ³ is C2alkynyl-Ar ¹ -1,2,3- triazole. In embodiments, R ³ is C1-4alkyl-1,2,3-triazole. [0043] In general, each L ¹ is a ligand (e.g., a neutral ligand or an anionic ligand) and can be independently selected from an N-heterocyclic carbene, a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six-membered cyclic group having 1 to 3 ring heteroatoms selected from O, N, and S. The five- or six-membered monocyclic groups can include 1 to 4 heteroatoms, 1 to 3 heteroatom, or 1 to 2 heteroatoms, for example, pyridine, pyridazine, pyrimidine, pyrazine, triazine, pyrrole, pyrazole, imidazoletriazole, pyran, pyrone, dioxin, and furan. The five- or six-membered monocyclic groups can be substituted with halo, C1-C20alkyl, C1-C20heteroalkyl, C5-C24aryl, C5-C24heteroaryl, and functional groups, including but not limited to, C1-C20 alkoxy, C5-C24 aryloxy, C2- C20alkylcarbonyl, C6-C24 arylcarbonyl, carboxy, carboxylate, carbamoyl, carbamido, formyl, thioformyl, amino, nitro, and nitroso. Phosphine and amine ligands can include primary, secondary, and tertiary phosphines and amines. The phosphine and amine ligands can include 0 to 3 alkyl groups, 1 to 3 alkyl groups, or 1 to 2 alkyl groups selected from C1- C20alkyl. The phosphine and amine ligands can also include 0 to 3 aryl or heteroaryl groups, 1 to 3 aryl or heteroaryl groups, or 1 to 2 aryl or heteroaryl groups selected from five- and six-membered aryl or heteroaryl rings. In embodiments, at least one L ¹ is an ether, such as, diethyl ether or THF, a phosphine, a NHC, or an amine, such as pyridine or triethyl amine. In embodiments, at least one L ¹ is a phosphine. In embodiments, each L ¹ is a phosphine. In embodiments, at least one L ¹ is a NHC. In embodiments, each L ¹ is a NHC. In embodiments, wherein m is 2 or 3, two L ¹ together can form a bidentate ligand. [0044] . In embodiments, each L ¹ is independently selected from C ₂ –C ₂₀ amide, C ₁ – C ₂₀ alkoxy, C ₆ –C ₂₀ aryloxy, C ₁ –C ₂₀ heteroaryloxy comprising 1 to 5 heteroatoms selected from O, N, and S, C ₁ –C ₂₀ alkylthio, C ₆ –C ₂₀ arylthio, C ₁ –C ₂₀ heteroarylthio comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one L ¹ is a C ₁ –C ₂₀ alkoxy. In embodiments, each L ¹ is a C ₁ –C ₅ alkoxy. In embodiments, at least one L ¹ independently is a C ₁ –C ₅ alkoxy. In embodiments, each L ¹ independently is a C ₁ –C ₅ alkoxy. [0045] When referring to a ligand, the term “amine” refers to a NH ₃ group, where 0, 1, 2, or 3 hydrogens can be replaced with an alkyl, cycloalkyl, or aryl group. When referring to a ligand, the term “amide” refers to a NR ₂ group, wherein each R is independently a hydrogen, alkyl, cycloalkyl, or aryl group. When referring to a ligand, the term “imine” refers to a NR group, wherein R is a hydrogen, alkyl, cycloalkyl, or aryl group

[0046] As used herein, the term “phosphine” refers to a -PH ₃ group, wherein 0, 1, 2, or 3 hydrogens can be replaced with an alkyl, cycloalkyl, or aryl group. As used herein “phosphite” refers to a P(OR) ₃ group, wherein each R can individually be alkyl, cycloalkyl, or aryl. As used herein, “phosphonite” refers to a PR(OR) ₂ group, wherein each R can individually be alkyl, cycloalkyl, or aryl. As used herein, “phosphinite” refers to a PR ₂ (OR) group, wherein each R can individually be alkyl, cycloalkyl, or aryl. As used herein, the term “diphosphine” refers to a P(R ₂ )-(CH ₂ ) _n -P(R ₂ ) group, wherein each R can individually be alkyl, cycloalkyl, or aryl and n can be 1, 2, 3, 4, or 5.

[0047] As used herein, “bidentate ligand” refers to a ligand that has two atoms that can coordinate directly to the metal center of a metal complex, e.g., a single molecule which can form two bonds to a metal center. Non-limiting examples of bidentate ligands include ethylenediamine, bipyridine, phenanthroline, and diphosphine.

[0048] A “neutral ligand,” as used herein, refers to a ligand that, when provided as a free molecule, does not bear a charge. Examples of neutral ligands include water, phosphines, ethers (e.g., tetrahydrofuran), and amines (e.g., pyridine, triethylamine, or the like). An “anionic ligand” refers to a ligand that, when provided as a free molecule, has a formal charge of -1. Examples of anionic ligands include, amides, chloride, methoxy, ethoxy, ispropoxy, tertbutoxy, tertbutyl, neopentyl, and cyclopentadienyl.

[0049] In general, m can be 1, 2, or 3. In embodiments, m is 1. In embodiments, m is 2. In embodiments, m is 3.

[0050] In general, each Ar ¹ can be independently selected from C ₆ -C ₂₂ aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one Ar ¹ is Ph. In embodiments, at least one Ar ¹ is a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.

[0051] Also provided herein are metallopolymers according to the foregoing disclosure having a structure of formula (lla) or (Mb): 32917/18298 b) wherein: each dashed line indicates an optional double bond; NHC is an N-heterocyclic carbene; each L ² is independently selected from an N-heterocyclic carbene, a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six-membered monocyclic group having 1 to 3 ring heteroatoms selected from O, N, or S; each R ⁴ is independently selected from H, C _1-10 alkyl, C _5- C ₈ cycloalkyl, and Ar ² , or both R ⁴ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; each R ⁵ is independently selected from H, C _1-10 alkyl, C _5- C ₈ cycloalkyl, and Ar ² or both R ⁵ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; each R ⁶ is independently selected from H, C _1-10 alkyl, C _5- C ₈ cycloalkyl, and Ar ² , or both R ⁶ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; n is 10 or more; m' is 1, 2, or 3; M is a transition metal; and, each Ar ² is independently selected from C ₆ -C ₂₂ aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. [0052] In general, each L ² can be independently selected from an N-heterocyclic carbene, a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six- membered monocyclic group having 1 to 3 ring heteroatoms selected from O, N, or S. In embodiments, at least one L ² is an ether, phosphine, a NHC, or an amine, such as pyridine or triethyl amine. In embodiments, at least one L ² is a phosphine. In embodiments, each L ² is a phosphine. In embodiments, at least one L ² is a NHC. In embodiments, each L ² is a NHC. In embodiments, wherein m’ is 2 or 3, two L ² together can form a bidentate ligand. [0053] . In embodiments, each L ² is independently selected from C2–C20amide, C1– C20alkoxy, C6–C20aryloxy, C1–C20heteroaryloxy comprising 1 to 5 heteroatoms selected from O, N, and S, C1–C20alkylthio, C6–C20arylthio, C1–C20heteroarylthio comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one L ² is a C1–C20alkoxy. In embodiments, each L ² is a C1–C5alkoxy. In embodiments, at least one L ² independently is a C1–C5alkoxy. In embodiments, each L ² independently is a C1–C5alkoxy. [0054] In general, m’ can be 1, 2, or 3. In embodiments, m’ is 1. In embodiments, m’ is 2. In embodiments, m’ is 3. [0055] In general, each R ⁴ can be independently selected from H, C1-10alkyl, C5- C8cycloalkyl, and Ar ² , or both R ⁴ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, or 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one R ⁴ is H. In embodiments, each R ⁴ is H. In embodiments, both R ⁴ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5- 7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, both R ⁴ , taken together with the carbon atoms to which they are attached, form an aryl. In embodiments, both R ⁴ , taken together with the carbon atoms to which they are attached, form a Ph or a substituted Ph. [0056] In general, each R ⁵ can be independently selected from H, C1-10alkyl, C5- C8cycloalkyl, and Ar ² , or both R ⁵ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, or 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one R ⁵ is H. In embodiments, at least one R ⁵ is C _1-5 alkyl. In embodiments, both R ⁵ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, both R ⁵ , taken together with the carbon atoms to which they are attached, form a 1,2,3-triazole. [0057] In general, each R ⁶ can be independently selected from H, C _1-10 alkyl, C _5- C ₈ cycloalkyl, and Ar ² , or both R ⁶ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one R ⁶ is H. In embodiments, each R ⁶ is H. In embodiments, both R ⁶ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5- 7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, both R ⁶ , taken together with the carbon atoms to which they are attached, form an aryl. In embodiments, both R ⁶ , taken together with the carbon atoms to which they are attached, form a Ph or a substituted Ph.

[0058] In general, each Ar ² can be independently selected from C -C aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one Ar ² is Ph. In embodiments, at least one Ar ² is a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.

[0059] Also provided herein is a metallopolymer according to the foregoing disclosure having a structure of formulas (IV), (V), (VI) or (VII): wherein: each Z is independently selected from C _1-22 alkyl, C _5- C ₈ cycloalkyl, and Ar ⁴ ; each Ar ⁴ is independently selected from C6-C22aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; and, Y is an electron rich species or an electron deficient species. [0060] In general, each Z can be independently selected from C1-22alkyl, C5-C8cycloalkyl, and Ar ⁴ . In embodiments, at least one Z is Ar ⁴ . In embodiments, each Z is Ar ⁴ . In embodiments, at least one Z is Ph. In embodiments, each Z is Ph. In embodiments, at least one Z is cyclohexyl. In embodiments, each Z is cyclohexyl. In embodiments, at least one Z is C1-6alkyl. In embodiments, each Z is C1-6alkyl. [0061] In general, each Ar ⁴ can be independently selected from C6-C22aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.. In embodiments, at least one Ar ⁴ is Ph. In embodiments, at least one Ar ⁴ is a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. [0062] In general, Y can be an electron rich species of the disclosure or an electron deficient species of the disclosure. In embodiments, Y is selected from , , , , , and . [0063] Also provided herein is a metallopolymer having a structure of (IIIa) or (IIIb): (IIIa); (IIIb) wherein: the dashed lines indicate optional double bonds; each L ³ is independently selected from a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six-membered monocyclic group having 1 to 3 ring heteroatoms selected from O, N, or S; each R ⁷ is independently selected from H, C1-10alkyl, C5-C8cycloalkyl, and Ar ³ , or both R ⁷ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; each R ⁸ is independently selected from H, C1-10alkyl, C5-C8cycloalkyl, and Ar ³ , or both R ⁸ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; each R ⁹ is independently selected from H, C1-10alkyl, C5-C8cycloalkyl, and Ar ³ , or both R ⁹ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S; n is 10 or more; m" is 1, 2, 3, or 4; M is a transition metal; and each Ar ³ is independently selected from C6-C22 aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. [0064] In general, each L ³ can be independently selected from a phosphine, a phosphite, a phosphonite, a phosphinite, an amine, an amide, an imine, an alkoxy, an aryloxy, an ether, a thioether, an alkylthio, an arylthio, and a five- or six-membered monocyclic group having 1 to 3 ring heteroatoms selected from O, N, or S. In embodiments, at least one L ³ is an ether, such as, diethyl ether or THF, a phosphine, or an amine, such as pyridine or triethyl amine. In embodiments, at least one L ³ is a phosphine. In embodiments, each L ³ is a phosphine. In embodiments, at least one L ³ is a ether. In embodiments, each L ³ is a ether. In embodiments, at least one L ³ is a thioether. In embodiments, each L ³ is a thioether. In embodiments, wherein m’ is 2 or 3, two L ³ together can form a bidentate ligand. [0065] . In embodiments, each L ³ is independently selected from C ₂ –C ₂₀ amide, C ₁ – C ₂₀ alkoxy, C ₆ –C ₂₀ aryloxy, C ₁ –C ₂₀ heteroaryloxy comprising 1 to 5 heteroatoms selected from O, N, and S, C ₁ –C ₂₀ alkylthio, C ₆ –C ₂₀ arylthio, C ₁ –C ₂₀ heteroarylthio comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one L ³ is a C ₁ –C ₂₀ alkoxy. In embodiments, each L ³ is a C ₁ –C ₅ alkoxy. In embodiments, at least one L ³ independently is a C ₁ –C ₅ alkoxy. In embodiments, each L ³ independently is a C ₁ –C ₅ alkoxy. [0066] In general, m" can be 1, 2, 3, or 4. In embodiments, m" is 1. In embodiments, m" is 2. In embodiments, m" is 3. In embodiments, m" is 4. [0067] In general, each R ⁷ can be independently selected from H, C1-10alkyl, C5- C8cycloalkyl, and Ar ³ , or both R ⁷ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one R ⁷ is H. In embodiments, each R ⁷ is H. In embodiments, both R ⁷ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5- 7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, both R ⁷ , taken together with the carbon atoms to which they are attached, form an aryl. In embodiments, both R ⁷ , taken together with the carbon atoms to which they are attached, form a Ph or a substituted Ph. [0068] In general, each R ⁸ can be independently selected from H, C1-10alkyl, C5- C8cycloalkyl, and Ar ³ , or both R ⁸ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one R ⁸ is H. In embodiments, at least one R ⁸ is C1-5alkyl. In embodiments, both R ⁸ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, both R ⁸ , taken together with the carbon atoms to which they are attached, form a 1,2,3-triazole. [0069] In general, each R ⁹ can be independently selected from H, C1-10alkyl, C5- C8cycloalkyl, and Ar ³ , or both R ⁹ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5-7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one R ⁹ is H. In embodiments, each R ⁶ is H. In embodiments, both R ⁹ , taken together with the carbon atoms to which they are attached, form an aryl, heteroaryl, 5- 7 membered cycloalkyl, or 5-7 membered heterocycloalkyl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, both R ⁹ , taken together with the carbon atoms to which they are attached, form an aryl. In embodiments, both R ⁹ , taken together with the carbon atoms to which they are attached, form a Ph or a substituted Ph. [0070] In general, each Ar ³ can be independently selected from C ₆ -C ₂₂ aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. In embodiments, at least one Ar ³ is Ph. In embodiments, at least one Ar ³ is a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S. [0071] In embodiments, the metallopolymer having a structure of (IIIa) or (IIIb) can have a structure of: , wherein n is 3 or more, m" is 4, each L ³ is a phosphine, and each R ¹⁰ is independently selected from C1-22alkyl and C5- C8cycloalkyl. In embodiments, each R ¹⁰ is C4-10alkyl. In embodiments, each R ¹⁰ is C6alkyl. Methods of Preparing the Metallopolymers of the Disclosure [0072] The disclosure further provides a method of preparing the metallopolymers of the disclosure. The method comprises admixing an azide-containing compound and an alkyne- containing compound under conditions sufficient to form a metallopolymer of the disclosure, wherein, one or both of the azide-containing compound and the alkyne-containing compound further comprises a transition metal. In embodiments, one or both of the azide- containing compound and the alkyne-containing compound further comprises an N- heterocyclic carbene. In embodiments, the method can further comprise admixing a catalyst with the azide-containing compound and the alkyne-containing compound. In embodiments, the admixing is performed in the absence of a catalyst. In embodiments, the catalyst comprises copper. In embodiments, the catalyst is a Cu(II) salt including a reducing agent, such as ascorbate or the like. In embodiments, the catalyst is CuX, wherein X is a halogen such as Cl, Br, or I. [0073] For example, Scheme 1 and 2 below show methods of preparing a metallopolymers of the disclosure in the absence of a catalyst. [0074] Scheme 1 [0075] Scheme 2

[0076] For example, Scheme 3 and 4 below show methods of preparing the metallopolymers of the disclosure with a catalyst (e.g., Cu(l)), wherein R can be an electron rich species or an electron deficient species, such

[0077] Scheme 3

[0079] In general, the azide-containing compound can include at least one azide functional group. In embodiments, the azide-containing compound includes two or more azide functional groups. In embodiments, the azide-containing compound includes two azide functional groups.

[0080] In general, the alkyne-containing compound can include at least one alkyne functional group. In embodiments, the alkyne-containing compound includes two or more alkyne functional groups. In embodiments, the alkyne-containing compound includes two alkyne functional groups.

[0081] In embodiments, the azide-containing compound includes the same number of azide functional groups (e.g., 1 or 2) as the alkyne-containing compound includes alkyne functional groups (e.g., 1 or 2). In embodiments, the azide-containing compound includes 1 azide functional group and the alkyne-containing compound includes 1 alkyne functional group. In embodiments, the azide-containing compound includes 2 azide functional groups and the alkyne-containing compound includes 2 alkyne functional groups.

[0082] In embodiments, the azide-containing compound comprises one or more transition metals of the disclosure, such as, 1, 2, 3, or 4 transition metals. In embodiments, the azide- containing compound comprises one transition metal. In embodiments, the azide-containing compound comprises two transition metal.

[0083] In embodiments, the alkyne-containing compound comprises one or more transition metals of the disclosure, such as, 1 , 2, 3, or 4 transition metals . In embodiments, the alkyne-containing compound comprises one transition metal. In embodiments, the alkyne-containing compound comprises two transition metal.

[0084] In general, the azide-containing compound and the alkyne-containing compound can be admixed under conditions sufficient to form the compound having a metallopolymer of the disclosure. In embodiments, the admixing comprises a molar ratio of the azide- containing compound and the alkyne-containing compound of about 1:1, respectively. In embodiments, the admixing comprises a molar ratio of the azide-containing compound and the alkyne-containing compound in a range of about 2:1 to about 1:2, or about 1.5:1 to about 1:1.5, or about 1.3:1 to about 1:1.3, or about 1.1:1 to about 1:1.1, respectively.

[0085] In some embodiments, the azide-containing compound and the alkyne-containing compound can be a single compound wherein the compound comprises both an azide functional group and an alkyne functional group. For example, Schemes 5 and 6 show various embodiments of polymerization reactions contemplated herein with compounds including both an azide functional group and an alkyne functional group.

[0086] Scheme 5

[0088] In embodiments wherein the admixing comprises a catalyst, the catalyst is present in an amount of 0.001 mol% to about 20 mol%, based on the mol% of the azide-containing compound. For example, the catalyst is present in an amount of about 1 mol%, about 2 mol%, about 5 mol%, about 10 mol%, or about 20 mol%. In general, when the admixing comprises a catalyst increasing the concentration of the catalyst can increase the rate the reaction to form metallopolymers of the disclosure.

[0089] In embodiments, the admixing of the azide-containing compound and the alkyne- containing compound can occur neat, for example, in cases where either or both of the azide-containing compound and the alkyne-containing compound is a liquid. In embodiments, the admixing of the azide-containing compound and the alkyne-containing compound can occur in solution. Suitable solvents include, but are not limited to, nonpolar aprotic solvents, such as, but not limited to, benzene, toluene, hexanes, pentanes, dichloromethane, trichloromethane, chloro-substituted benzenes, deuterated analogs of the foregoing and combinations of the foregoing. As will be understood by one of ordinary skill in the art, polar aprotic solvents may also be suitable provided they do not compete with the iCIick reaction or the coordination of ligands at the metal center. Suitable polar aprotic solvents can include, but are not limited to, diethyl ether, ethyl acetate, acetone, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, deuterated analogs of the foregoing, and combinations of the foregoing.

[0090] The admixing of the azide-containing compound and the alkyne-containing compound can occur at any suitable temperature for any suitable time. It is well understood in the art that the rate of a reaction during admixing can be controlled by tuning the temperature. Thus, in general, as the reaction temperature increases the reaction time can decrease.

[0091] The polymerization of the metallopolymers of the disclosure can be carried out at, for example, ambient temperatures (e.g., about 20°C to about 25°C) at dry conditions (e.g., about 0-1% RH) under an inert atmosphere (e.g., nitrogen or argon). Polymerization temperatures can be in a range of about -80°C to about 100°C, about -70°C to about 80°C, about -50°C to about 75°C, about -25°C to about 50°C, about 0°C to about 35°C, about 5°C to about 30°C, about 10°C to about 30°C, about 15°C to about 25°C, about 20°C to about 30°C, or about 20°C to about 25°C, for example, about 0°C, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, or about 35°C. Reaction times can be instantaneous or otherwise until completion. The progress of the reaction can be monitored by standard techniques, e.g., nuclear magnetic resonance (NMR) spectroscopy. In embodiments, the reaction times are in a range of about 30 seconds to about 72 hours, about 1 minute to about 72 hours, about 5 minutes to about 72 hours, about 10 minutes to about 48 hours, about 15 minutes to about 24 hours, about 1 minute to about 24 hours, about 5 minutes to about 12 hours, about 10 minutes to about 6 hours, about 20 minutes to about 1 hour, about 30 minutes (min) to about 12 hours (h), about 1 hour to about 10 hours, about 1 hour to 3 hours, about 25 min to about 6 h, or about 30 min to about 3 h, for example, about 30 seconds, 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min,

40 min, 45 min, 50 min, 55 min, 60 min, 75 min, 90 min, 105 min, 2 h, 3 h, 4 h, 5 h, 6 h, 12 h, 18 h, 24 h, 36 h, 48 h, 60 h, or 72 h. Polymerization times will vary, depending on the particular monomer and the metal complex.. It is well understood in the art that when the polymerization time is increased and/or the temperature is increased, the products are likely high molecular weight products, and when the polymerization time is decreased and/or the temperature is decreased, the products are likely low molecular weight products.

[0092] Polymerization may be terminated at any time by addition of a solvent effective to precipitate the polymer, for example, methanol. The precipitated polymer may then be isolated by filtration or other conventional means.

[0093] The molecular weight of the metallopolymers can be small, equivalent to oligomers of three to ten repeating units (e.g., wherein n is 3 to 10, for example, 3, 4, 5, 6, 7, 8, 9, or 10), or the molecular weights can be of any size up to tens and hundreds of thousands or millions in molecular weight, for example, in a range of about 200 Da to about 5,000,000 Da, about 500 Da to about 4,000,000 Da, about 1,000 Da to about 3,000,000 Da, about 5,000 Da to about 2,000,000 Da or about 10,000 to about 1,000,000 Da (e.g., where n is greater than 3). As used herein, the molecular weights are provided in number average molecular weights determined by gel permeation chromatography relative to polystyrene standards. EXAMPLES [0094] Materials and Methods: [0 [0096] TRANS-4-(AZIDOMETHYL)PHENYL-BIS-TRI-N-BUTYLPHOSPHINE(4- FLUOROPHENYLACETYLIDE)PLATINUM(II) (4-F). Complex 3 (0.194 g, 0.025 mmol) and 1-fluoro-4-ethynylbenzene (0.041 g, 0.034 mmol) were dissolved in HNEt2 (15 ml). The solution was heated to 60 °C for 7 h. The solvent was then removed in vacuo. The products were washed with hexanes to remove salts and the solvent was removed in vacuo. Fractional column chromatography on silica gel with hexanes/DCM (1:1) as the eluent was employed to purify 4-F as a colorless oil. Yield: 0.172 g, 79.8%. ¹ H NMR (500 MHz, CDCl ₃ , 25 °C, δ (ppm)): 7.33 (d, ³ J _HH = 7.7 Hz, 2H, HC ₂ ), 7.20 (dd, ³ J _HH = 5.5 Hz, ⁴ J _HH = -2.75 Hz 2H, HC ₁₃ ), 6.91 (d, ³ J _HH = 7.7 Hz, 2H, HC ₃ ), 6.87 (t, ³ J _HH = 8.8 Hz, 2H, HC ₁₄ ), 4.15 (s, 2H, HC ₅ ), 1.70 (m, 12H, HC ₆ ), 1.48 (m, 12H, HC ₇ ), 1.34 (sex, ³ J _HH = 7.1 Hz, 12H, HC ₈ ), 0.88 (t, ³ J _HH = 7.7 Hz, 18H, HC ₉ ). ¹³ C{ ¹ H} NMR (500 MHz, CDCl ₃ , 25 °C, δ (ppm)): 161.3 (C ₁₅ ), 157.6 (C ₁ ), 139.1 (C ₂ ), 131.9 (C ₁₃ ), 127.5 (C ₄ ), 127.4 (C ₃ ), 125.5 (C ₁₂ ), 114.7 (C ₁₄ ), 108.6 (C ₁₁ ), 55.3 (C ₅ ), 26.0 (C ₇ ), 24.3 (C ₈ ), 22.8 (C ₆ ), 13.8 (C ₉ ). ³¹ P{ ¹ H} NMR (121.4 MHz, CDCl ₃ , 25 °C, δ (ppm)): 2.0 (s, ¹ J _PtP = 1301 Hz). ¹⁹ F NMR (282 MHz, CDCl ₃ , 25 °C, δ (ppm)): -117.2 (m). FTIR (NaCl, cm ^-1 ): 3043 (w), 2960 (s), 2929 (s), 2873 (s), 2100 (s), 1587 (w), 1500 (s), 1462 (m), 1415 (m), 1381 (m), 1344 (w), 1232 (m), 1205 (s), 1151 (w), 1091 (w), 906 (m), 831 (s), 791 (m), 737 (m), 526 (m). Anal. Calcd. (%) for C ₃₉ H ₆₄ FN ₃ P ₂ Pt: C, 55.05; H, 7.58; N, 4.94. Found: C, 55.18; H, 7.30; N, 4.67. HRMS (ESI): m/z calcd. for C ₃₉ H ₆₄ FN ₃ P ₂ PtNa, [M+Na] ⁺ : 873.4103; found: 873.4091. [0097] [0098] POLY[TRANS-4-(AZIDOMETHYL)PHENYL-BIS-TRI-N-BUTYLPHOSPHINE(4- NITROPHENYLACETYLIDE)PLATINUM(II)] (5-NO ₂ ). Monomer 4-NO ₂ (0.060 g, .0680 mmol) and CuOAc (0.003 g, 32 mol%) where dissolved in CDCl ₃ at room temperature. After 24 h the solution was filtered through Celite® and all volatiles were removed in vacuo to give 5-NO2 as a red solid. Yield: 46.0 mg, 77%. ¹ H NMR (500 MHz, CDCl3, 25 °C, δ (ppm)): 8.96 (d, ³ J _HH = 8.5 Hz, 2H, HC ₈ ), 8.27 (d, ³ J _HH = 8.5 Hz, 2H, HC ₇ ), 7.04-7.67 (m, 4H, HC _2,3 ), 5.78 (s, 2H, HC10), 5.61 (s, 2H, HC10), 5.54 (s, 2H, HC10), 4.26 (s, 2H, HC10), 1.23 (m, 36H, HC11- 13), 0.82 (t, ³ JHH = 6.9 Hz, 18H, HC14). ³¹ P{ ¹ H} NMR (121.4 MHz, CDCl3, 25 °C, δ (ppm)): 9.2 (s), 4.9 (s), 0.4 (s, ¹ JPtP = 1303 Hz), -0.1 (s), -0.2 (s), -0.6 (s). FTIR (NaCl, cm ^-1 ): 2958 (w), 2923 (w), 2870 (w), 1595 (w), 1512 (w), 152 (w), 1383 (w), 1329 (w), 1107 (w), 1091 (w), 903 (w), 852 (w). MS (MALDI-TOF): (m/z), 1761.166, 26632.005, 3510.859, 4389.129, 5266.945, 6144.693, DP=9. [0099] [0100] POLY[TRANS-4-(AZIDOMETHYL)PHENYL-BIS-TRI-N-BUTYLPHOSPHINE(4- FLUOROPHENYLACETYLIDE)PLATINUM(II)] (5-F). Monomer 4-F (0.056 g, 0.0630 mmol) and CuOAc (0.0014 g, 20 mol%) where dissolved in CDCl3 at room temperature. After 24 h the solution was filtered through Celite® and all volatiles were removed in vacuo to give 5-F as a colorless solid. Yield: 44.1 mg, 82%. ¹ H NMR (500 MHz, CDCl3, 25 °C, δ (ppm)): 8.65 (s, 2H, HC8), 7.50 (s, 2H, HC7), 6.88-7.80 (m, 6H, HC2,3,7), 5.74 (s, 2H, HC10), 1.10-1.60 (m, 36H, HC11-13), 0.82 (t, ³ JHH = 7.1 Hz, 18H, HC14). ³¹ P{ ¹ H} NMR (121.4 MHz, CDCl3, 25 °C, δ (ppm)): 2.1 (s), -2.2 (s, ¹ JPtP = 1316 Hz), -2.6 (s), -3.3 (s). ¹⁹ F NMR (282 MHz, CDCl3, 25 °C, δ (ppm)): -114.3 (m), -118.4 (m). FTIR (NaCl, cm ^-1 ): 2955 (s), 2925 (s), 2862 (s), 2042 (w), 2016 (w), 1591 (m), 1479 (m), 1461 (s), 1412 (m), 1375 (m), 1196 (m), 1092 (m), 902 (s), 749 (s), 719 (s), 689 (s). MS (MALDI-TOF): (m/z), 25452, 3397, 4249.421, 5101.725, 5952.860, 6803979 7654636 8506143 9356611 DP=11 [0101] [0102] TRANS-4-AZIDOPHENYL-BIS-TRI-N-BUTYLPHOSPHINE(2-ETHYNYL-9,9- DIOCTYL-9H-FLUORENE)PLATINUM(II) (1). Compound 3 (0.216 g, 0.256 mmol) and 2- ethynyl-9,9-dioctyl-9H-fluorene (0.111 g, 0.269 mmol) were taken into DIPA (10 mL) and heated at 60 °C for 20 h. The solvent was removed in vacuo and the resulting mixture of compounds was triturated with hexanes and purified on a silica column with hexanes/DCM (1:1) as the eluent to yield the product (0.225 g, 77.8%). ¹ H NMR (500 MHz, CDCl3, 25 °C, δ (ppm)): 7.61 (d, ³ JHH = 7.3 Hz, 1H, HC22), 7.52 (d, ³ JHH = 7.8 Hz, 1H, HC15), 7.32 (d, ³ JHH = 8.3 Hz, 2H, HC2), 7.30 (m, 1H, HC19), 7.28 (s, 1H, HC12), 7.27 (m, 1H, HC21), 7.25 (m, 1H, HC16), 7.24 (m, 1H, HC20), 6.73 (d, ³ JHH = 8.3 Hz, 2H, HC3), 1.90 (dquin, ³ JHH = 13.2, 4.9 Hz 4H, HC24), 1.77 (m, 12H, HC5), 1.53 (m, 12H, HC6), 1.39 (sex, ³ JHH = 7.3 Hz, 12H, HC7), 1.21 (sept, ³ JHH = 7.3 Hz, 4H, HC26), 1.13 (m, 4H, HC27), 1.10 (m, 4H, HC28), 1.04 (m, 4H, HC29), 1.04 (m, 4H, HC30), 0.91 (t, ³ JHH = 7.3 Hz, 18H, HC8), 0.82 (t, ³ JHH = 7.3 Hz, 6H, HC31), 0.62 (dm, ³ JHH = 36.1 Hz, 4H, HC24). ¹³ C{ ¹ H} NMR (500 MHz, CDCl3, 25 °C, δ (ppm)): 153.5 (C1), 150.7 (C18), 150.2 (C13), 139.8 (C14), 139.7 (C2), 137.9 (C17), 133.0 (C4), 129.5 (C16), 127.8 (C11), 126.5 (C12), 126.3 (C20), 125.3 (C21), 122.7 (C19), 119.3 (C22), 119.0 (C15), 117.8 (C3),111.4 (C10), 54.7 (C23), 40.5 (C24), 31.8 (C27), 30.2 (C29), 29.3 (C30), 29.3 (C28), 26.2 (C6), 24.4 (C7), 23.8 (C25), 22.8 (C5), 22.6 (C26), 14.0 (C31), 13.8 (C8). ³¹ P{ ¹ H} NMR (121.4 MHz, CDCl3, 25 °C, δ (ppm)): 1.43 (s, ¹ JPtP = 1296 Hz). FTIR (NaCl, cm ^-1 ): 2956 (s), 2929 (s), 2856 (s), 2412 (w), 2117 (s), 2079 (s), 1604 (m), 1566 (w), 1465 (m), 1384 (m), 1286 (m), 1210 (w), 1129 (w), 1092 (m), 1053 (w), 1011 (w), 905 (w), 809 (m), 739 (m). [0103] [0104] POLY[TRANS-4-AZIDOPHENYL-BIS-TRI-N-BUTYLPHOSPHINE(2-ETHYNYL- 9,9-DIOCTYL-9H-FLUORENE)PLATINUM(II)] (4). Monomer 1 (0.247 g, 0.219 mmol) and CuOAc (0.005 g, 20 mol%) were dissolved in DCM (5 mL). The reaction was allowed to progress for 10 d. The solvent was removed in vacuo and the solid was taken up into benzene and filtered to remove CuOAc to yield 0.195 g, 79%. ¹ H NMR (500 MHz, CDCl ₃ , 25 °C, δ (ppm)): 7.10-9.45 (aromatic, 11H), 0.41-2.30 (aliphatic, 88H). ³¹ P{ ¹ H} NMR (121.4 MHz, CDCl ₃ , 25 °C, δ (ppm)): 9.43 (s), 4.30 (s), 3.79 (s), 2.85 (s), 2.00 (s), 1.12 (s), 4.29 (s, ¹ J _PtP = 1325 Hz), -4.89 (s). FTIR (NaCl, cm ^-1 ): 3408 (br, w), 3174 (br, w), 2954 (m), 2926 (s), 2854 (m), 1734 (w), 1608 (w), 1466 (m), 1385 (s), 1263 (m), 1091 (m), 1024 (m), 899 (w), 800 (m), 739 (m). [0105] Example 1 - Synthesis of Metallopolymer Precursors

[0106] Metallopolymer precursor experiments with commercially available cyclooctyne are conducted. The first metal centers contemplated are three metal-azide complexes from groups 11 (Ph ₃ PAuN ₃ ), 10 (trans-( Pr ₃ P) ₂ PtPhN ₃ ), and 6 ((bipy)(C ₃ H ₅ )W(CO) ₂ N ₃ ), wherein “bipy” refers to 2,2’-bipyridine. The initial experiments are intended to give an outlook at the breadth of the reaction scope possible across the transition metals.

[0107] Employing a methodical approach, a second cycloaddition across the commercially available 1,5-cycloctadiyne is employed. However, previously reported conditions showed that a first cycloaddition takes place rapidly, but the second cycloaddition in fact does not occur (Yang, et al. , OrganometalUcs 2017, 36, 1352-1357). This surprising result serves as a reminder that subtle steric and electronic factors greatly influence the iCIick reaction, thus requiring a more thorough investigation of these reactions and subtle changes to the compounds therein. Due to the alkyne strain of the cyclic dialkyne, the iCIick reaction is expected to readily occur.

[0108] Example 2 - Synthesis of Metallopolymers

[0109] Conjugated Chromophores : The conjugate chromophores are synthesized by using Ru(ll) centers, such as the scheme above shows. These complexes can potentially display unique and useful photoredox properties, in addition to giving rise to a new class of photoluminescent materials.

[0110] Solubility is often a challenge in metallopolymer synthesis. However, one advantage of the iCIick reaction is that it is modular, thus adjusting for solubility challenges can be achieved. Addressing solubility concerns, functionalized and highly soluble cyclooctadiyne is used to produce an advantageously soluble metallopolymer. Cyclooctadiyne is mixed with frans-(depe) ₂ Ru(N ₃ )2 (depe = 1,2-bis(diethylphosphino)ethane) resulting in a cascade of iCIick reactions to form the Ru-metallopolymer above. Initial characterization will include standard photophysical interrogation (e.g., UV-vis absorbance, or fluorescence), DOSY NMR, GPC, followed by incorporating the material into a solid state OLED.

[0111] Example 3 - Metallopolymer Precursors including NHCs

[0112] Table 1

[0113] Table 1 shows the various differences in photoluminescent properties of two Pt(ll) complexes differing only by the type of ligand employed, i.e., a phosphine versus a N- heterocyclic carbene. \=J

[0114] Using a one-pot method, the Pt-NHC precursors that feature two different NHC ligands shown above are synthesized according to previous reports (Winkel et al., Dalton Trans. 2014, 43, 17712-17720). Treating the /rans-(NHC)2PtCl2 with TIPS mono-protected phenyl acetylide under Hagihara reaction conditions (Blue Phosphorescent trans-N- Heterocyclic Carbene Platinum Acetylides: Dependence on Energy Gap and Conformation, James D. Bullock, Silvano R. Valandro, Amanda N. Sulicz, Charles J. Zeman, Khalil A. Abboud, and Kirk S. Schanze; The Journal of Physical Chemistry A 2019 123 (42), 9069- 9078) provides the Pt-acetylides shown above. The TIPS groups are deprotected and treated with a linking diazide under Cu(l) catalytic conditions to initiate iCIick polymerization. By retaining the Pt-acetylide, the resulting metallopolymers will exhibit efficient, intense, and tunable phosphorescence.

[0115] Example 4 - Synthesis of Metallopolymers including NHCs

[0116] Synthesis of platinum in-chain conjugated metallopolymers via iCIick can lead to further interesting photoluminescence properites. In the mild and versatile iCIick approach, the metal centers are incorporated into the conjugated polymer backbone and further tune the photophysical properties of the resulting metallopolymer. The Pt-acetylide functionality, important in producing excellent photophysics, is preserved, but at the same time allows the metal centers to be linked via iCIick. The Pt-bis-acetylides are coupled with a,w-diazides in Cu(l) catalyzed cycloadditions shown above. Previous studies on Pt-acetylide based polymers indicate the platinum is bound to the polyyne via a strong o-bond, thus yielding very robust polymers (Wong, Macromol. Chem. Phys. 2008, 209, 14-24; Wong et al., Macromolecules 2002, 35, 3506-3513). Unique to the iCIick approach of this disclosure, the metallopolymers are modified by the choice of the linking diazide unit. The scheme above depicts several choices of linking units that span both donor and acceptor properties. Advantageously, the tunability of the R-group above, including either electron donor species or electron acceptor species, allows for access to a wide array of metallopolymers, and permits the fine-tuning of their optical properties. Depicted in the syntheses are benzimidazole NHC ligands; however, a wide-variety of NHC ligands are plausible. The need for Cu(l) catalyzed reactions can be eliminated in certain cases.

[0117] Metallopolymer precursors with both azide and alkyne functionalities: The asymmetric platinum(ll) complexes contain a polyyne moiety conjugated to an aryl azide. Previously reported alkyne-azide platinum complexes have been reported and such methods are employed to synthesize the precursors (Schanze et al., J. Am. Chem. Soc. 2007, 129, 8958-8959; Winkel et al., Dalton Trans. 2014, 43, 17712-17720; Wong et al.,

Macromolecules 2002, 35, 3506-3513). The experiments shown above show a synthetic methodology for the preparation of in-chain metallopolymers of the disclosure. These reactions can be fine-tuned for different desired opto-electric materials properties.