FLUOROPHTHALOCYANINES WITH AGGREGATING PROPERTIES AND CATALYTIC DRIVEN PATHWAY FOR OXIDIZING THIOLS

STATEMENT OF GOVERNMENT SUPPORT

[0001] The United States government may hold license and/or other rights in this invention as a result of financial support provided by governmental agencies in the development of aspects of the invention. Parts of this work were supported by a grant from the National Science Foundation, Grant No. CBET-023381 1 , and contracts with the U.S. Army, Contract Nos. DAAE30-03-D-1015-0032 and W15-QKN- 10-0503-002.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of U.S. Provisional Application Nos. 61/409,049, filed November 1 , 2010, and 61/469,232, filed March 30, 2011. The entire content of the foregoing provisional patent applications is incorporated herein by reference.

BACKGROUND

Technical Field

[0003] The present invention relates to molecules that lack carbon hydrogen bonds, bind metals and exhibit variable aggregation due to partial steric hindrance, in particular, the present invention relates to fluoroalkylated fluorophthaiocyanine molecules, which exhibit novel asymmetry and tunable π-π stacking interactions. The present invention further relates to phthalocyanine molecules that lack carbon hydrogen bonds, bind metals, and broaden the reactivity spectrum of a catalyst while suppressing its nucleophilic, electrophilic and radical degradation pathways.

Background Art

[00Θ4] Phthalocyanines bearing perfluoroalkyl groups exhibit useful properties, such as surface coverage, coatings and photosensitizing properties. One structural defining property is the presence of perfluoroalkyl groups that impart solubility and variable steric hindrance that precludes the aggregation of the planar phthalocyanine macrocycle via known π-π stacking interactions. Another structural defining property, as depicted in FIG. 1 (a), is the symmetric characteristic of peril uorophthalocyanines known in the art. The symmetric perfluorophthalocyanines of the prior art thereby exhibit a four-fold axis of rotation. [0005] As shown in FIG. 1(a), due to the structural properties of the classical perfluorophthalocyanines, stacking is exhibited both in solution and in the solid state. This stacking characteristic of classical perfluorophthalocyanines severely limits their solubility in organic solvents and, thus, also limits their processability. Such molecules are generally produced via the template tetramerization of various fluorinated precursors, the most common one being the tetrafluorophthalonitrile, as shown in FIG. 2(a).

[0006] Other exemplary molecules of the prior art are depicted in FIGS. 2(a)-(f). Specifically, FIG. 2(a) shows tetrafluorophthalonitrile, FIG. 2(b) shows a F _{i 6} PcM, a metalio- perfluorophthalocyanine, M = metal ion in the +2 oxidation state, FIG. 2(c) shows a 4,5- bis(trifluoromethyl)-phthaIonitrile (see, e.g., Pawlowski, G. et ai., Synthetic Communications, 1 1, 351 (1981) and Chambers, R. D. et al., Tetrahedron, 54, 4949, (1998)), FIG. 2(d) shows a metallo-2,3,9,10, 16, 17,23 ₅ 24-octakis-(trifluoromethyl)-phthalocyanine, F2 ₄ H ₈ PcM (see, e.g., Pawlowski, G. et al., Synthetic Communications, 11 , 351 (1981 )), FIG. 2(e) shows a perfluoro-4,5-diisopropyl-phthalonitriIe (see, e.g., Gorun, S. 3V1. et al., Journal of Fluorine Chemistry, 91, 37 (1998)), and FIG. 2(f) shows a metallo-perfIuoro-2,3,9,10,16, 17,23,24- octakis-(isopropyl)-phthalocyanine, F6 ₄ PcM (see, e.g., Bench, B. A. et ai., Angew. Chem. Int. Ed., 41, 747 (2002) and Bench, B. A. et al., Angew. Chem. Int. Ed., 41 , 750 (2002)).

[0007] The introduction of iso-perfluoroalkyl groups generally results in the formation of perfluoroalkyl perfluorophthaiocyanines that minimize aggregation via an increased degree of steric hindrance. In addition, a significant higher degree of solubility in organic solvents may result. The structural prototype for such molecules is shown in FIGS. 2(e)-(f).

[0008] However, a need remains for fluorophthalocyanines which exhibit asymmetric properties and enable stacking, while permitting a high degree of solubility and aggregation.

[0009] These and other needs are addressed by the systems and methods of the present disclosure.

SUMMARY

[0010] In accordance with embodiments of the present disclosure, classes of fluoroalkylated fluorophthalocyanine molecules, exhibiting novel asymmetry and tunable π-π stacking interactions are provided. The metal remains capable of binding additional molecules. Such aggregation may help improve or trigger new surface properties of the materials, alone or in combination with others. [0011] In a further implementation of the present disclosure, an organic-based, thermally and chemically robust molecule that may suggest ways to design materials refractory to nucieophilic, electrophilic or radical attack while exhibiting useful aerobic catalytic properties is provided.

[0012] Other objects, features and functionalities of the present disclosure will become apparent from the following detailed description considered in conjunction with the accompanying drawings. It is to be understood, however, that the narrative description and drawings are designed as exemplary teachings only and not as a definition of the limits of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] To assist those of skill in the art in making and using the disclosed systems/methods, reference is made to the accompanying figures, wherein:

[0014] FIG. 1 illustrates general structures of a) symmetric and b) asymmetric phthalocyanines;

[0015] FIGS. 2(a)-(f) illustrate prior art molecules, including a) tetrafluorophthalonitrile; b) FjePcM, a metaUo-perfluorophthalocyanine, M = metal ion in the +2 oxidation state, c) 4,5-bis(trifluoromethyl)-phthalonitrile, d) metallo-2,3,9, 10, 16, 17,23,24-octakis-

(trifluoromethyl)-phthalocyanine, F24H8PC , e) perfluoro-4,5-diisopropyI-phthalonitrile, f) metallo-perfluoro-2,3,9, 10, 16, 17,23 ,24-octakis-(isopropyl)-phthaIocyanine, Fe ₄ PcM;

[0016] FIGS. 3(a)-(e) depict exemplary classes of molecules described herein, including a) metallo-2,3,9, 10, 16, 1 7,23,24-octakis-(trifluoromethyl)-tetrafluorophthalocyanine,

F2SH4PCM, b) metallo-perfluoro- l,2,4-triisopropyl-phthalocyanine, F34PCM, c) metallo- perfluoro- 1 , 2,4,8, 10, 1 1 -hexa-isopropyl-phthalocyanine, FsiPc'M, d) metallo-perfluoro- 2,3,9, 10-tetraisopropyl-phthalocyanine, F ₄₀ PcIv], and e) metallo-perfluoro-2,3,9, 10, 16, 17- hexaisopropyl-phthalocyanine, F52Pc"M;

[0017] FIG. 4 depicts an exemplary synthesis scheme pattern for exemplary embodiment F28H4PCM, with numbering of compounds;

[0018] FIGS. 5(a)-(d) illustrate X-ray structures of a) 1 ,2-bis(trifluoromethyl)-3-nitro-4,5- dimethylbenzene, b) l ,2-bis(trifluoromethyl)-3-fluoro-4,5-dimethylbenzene, c) 4,5- bis(trifluoromethy])-3-fluorophthalic acid, and d) 4,5-bis(trifluoromethyl)-3- fluorophthalonitrile; [0019] FIGS. 6 shows the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F _2g H ₄ PcZn;

[0020] FIGS. 7(a)-(c) display UV-Vis data comparison in acetone of partially aggregated b) F ₂ gH ₄ PcZn with sterically non-hindered a) F]gPcZn and sterically hindered c) F6 ₄ PcZn;

[0021] FIGS. 8(a)-(d) display UV-Vis electronic absorption spectra of F ₂ 8H ₄ PcZn, depicting strong solvent-dependent aggregation: a) chloroform, monomer (minimal aggregation); b) ethyl acetate, mostly monomer; c) acetone, intermediate aggregation; d) ethanol, mostly aggregated;

[0022] FIGS. 9(a)-(c) illustrate a) the X-ray structure of F ₂₈ H ₄ PcZn(CH ₃ CN) showing metal-coordinated acetonitrile, b) the top view of the π-π stacking region of two adjacent molecules of F ₂ gH4PcZn, and c) the side view of the aggregation of F^FLiPcZn in solid state (bal 1-an d- stick representation);

[0023] FIGS. 10 shows the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F ₂ sH ₄ PcCo;

[0024] FIG. 1 1 depicts an exemplary synthesis scheme for production of asymmetric F ₃₄ PcM and F5 ₂ Pc'M, showing the results of the combination of precursors P0 and P3;

[0025] FIG. 12 shows the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F ₃₄ PcZn;

[0026] FIGS. 13(a)-(b) display the UV-Vis electronic absorption spectra of F3 ₄ PcZn showing solvent-dependent aggregation: a) chloroform, monomer; b) ethanol, significant degree of dimerization;

[0027] FIGS. 14 shows the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F5 ₂ Pc'Zn;

[0028] FIG. 15 shows the X-ray structure of F ₅₂ Pc'Zn(OPPh ₃ );

[0029] FIG. 16 illustrates the aggregation in solid state (side view) of F ₅₂ Pc'Zn;

[003Θ] FIG. 17 shows the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M] for F ₃₄ PcCo;

[0031] FIGS. 18(a)-(b) illustrate a) the aggregation in solid state (side view) of F34PCC0, and b) a top view of the π-π stacking region of two adjacent molecules of F ₃₄ PcCo;

[0032] FIG. 19 shows the X-ray structure of F ₃₄ PcCo(CH ₃ CN); [0033] FIG. 20 shows the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M ^~ for F ₅₂ Pc'Co;

[0034] FIGS. 21 (a)-(d) depict a) a ball and-stick representation of F ₃₄ PcZn(H ₂ 0) ^• ((CH ₃ ) ₂ CO) ₂ , b) a van der Waais representation of F ₃₄ PcZn(H ₂ 0 ((CH3) ₂ CO)2, c) aggregation in solid state of F34PcZn(H ₂ 0) (side view), and d) a top view of the π-π stacking region of two adjacent molecules of F ₃ PcZn(H ₂ 0);

[0035] FIG. 22 illustrates the X-ray structure of F ₃₄ PcZn(H ₂ 0);

[0036] FIG. 23 illustrates an exemplary synthesis scheme for production of asymmetric F40PCM and Fs ₂ Pc"M, showing the results of the combination of precursors P0 and P2;

[0037] FIG. 24 shows the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F ₄₀ PcZn;

[0038] FIG. 25 illustrates the X-ray structure of F ₄₀ PcZn(OPPh ₃ );

[0039] FIGS. 26(a)-(b) illustrate a) the aggregation in solid state (side view) of F4oPcZn(OPPh ₃ ), and b) a top-down view of the π-π stacking region of two adjacent molecules of F4oPcZn;

[0040] FIGS. 27(a)-(b) display the UV-Vis electronic absorption spectra of F^PcZn showing solvent-dependent aggregation: a) chloroform, monomer; b) ethanol, strong aggregation;

[0041] FIG. 28 shows the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F ₅₂ Pc"Zn;

[0042] FIG. 29 shows the measured exact mass spectrum (positive ion ESI) and isotope pattern of [M + H] ⁺ for F ₄₀ PcCo;

[0043] FIG. 30 illustrates the X-ray structure of F ₀ PcCo(H ₂ O);

[0044] FIGS. 3 l (a)-(b) show the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M] ^~ for Fs ₂ Pc"Co;

[0045] FIGS. 32(a)-(b) display the UV-Vis electronic absorption spectra of F ₅₂ Pc"Co showing solvent-dependent aggregation: a) chloroform, slightly aggregated; b) tetrahydrofuran, increased degree of aggregation; [0046] FIGS. 33(a)-(b) illustrate a) exemplary cobalt phthalocyanines, and b) F64pcCo(0 ₂ ) reaction intermediate, drawn based on the X-ray structure of F ₆₄ PcCo-((CH ₃ ) ₂ CO) ₂ ;

[0047] FIGS. 34(a)-(b) display a) a plot of Pc(Co(Il)/Co(l)) reduction potentials vs. the sum of substituents Hammett σ constants, and b) 0 ₂ consumption in the catalyzed autooxidation of 2-mercaptoethanoi in aqueous tetrahydrofuran;

[0048] FIGS. 35(a)-(b) display a) ESR spectrum of F ₆ PcCo in acetone, and b) ESR spectrum of F^PcCo in acetone/N-methyl imidazole;

[0049] FIG. 36 illustrates the UV-Vis titration of F ₆₄ PcCo with aqueous NaOH in THF;

[0050] FIG. 37 shows the ratio of catalysts Q-bands intensities after 5 h and 24 h, relative to initial intensities, taken as a measure of catalyst stability, during the autooxidation of 2- mercaptoethanol in aqueous tetrahydrofuran;

[0051] FIGS. 38(a)-(c) display UV-Vis monitored catalyst stability of a) F ₁₆ PcCo, b) F6 ₄ PcCo, and c) H^PcCo during the autooxidation of 2-mercaptoethanol in aqueous tetrahydrofuran; and

[0052] FIG. 39 illustrates the ⁽ ¾ consumption in the catalyzed oxidation of perf!uoro benzenethiol, with the inset depicting the parallel reaction of thioether- thiol formation via nucleophilic attack in the absence of the catalyst.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

[0053] The following is a detailed description of the invention provided to aid those skilled in the art in practicing the present invention. Those of ordinary skill in the art may make modifications and variations in the embodiments described herein without departing from the spirit or scope of the present invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for describing particular embodiments only and is not intended to be limiting of the invention. All publications, patent applications, patents, figures and other references mentioned herein are expressly incorporated by reference in their entirety. FLUOROALKYLATED FLUQROPHTHALQCYANINES

[Θ054] In accordance with embodiments of the present disclosure, classes of fluoroalkylated fluorophthalocyanine molecules, exhibiting novel asymmetry and tunable π-π stacking interactions are provided. In particular, a composition is disclosed including a phthalocyanine molecule, the phthalocyanine molecule exhibiting an asymmetric orientation and the phthalocyanine molecule exhibiting tunable π-π stacking. The phthalocyanine molecule is generally a fluoroalkylated fluorophthalocyanine molecule, is capable of aggregation and is adapted to form intermolecular interactions. Further, the phthalocyanine molecule may be produced by template tetramerization and exhibits tunable π-π stacking in a solution state and a solid state. The asymmetric orientation of the disclosed phthalocyanine provides advantageous properties, including increased solubility, variability and tenability in aggregation, compatibility with polymers, variable film forming properties, a variable optical property, and tunable magnetic and electronic interactions.

[0055] In accordance with embodiments of the present disclosure, a method for forming a composition is also provided. The disclosed method generally involves introducing a phthalocyanine molecule, the phthalocyanine molecule exhibiting an asymmetric orientation and tunable π-π stacking.

[0056] Similar to the case of the FiePcM (Pc = phthalocyanine and M = metal), F ₂ 4HgPc!Vl, and F64PcM molecules, depicted in FIGS. 2(a)-(d), the new classes of molecules, F ₂ sH ₄ PcM, F34PCM, F ₅ 2Pc'M, and F ₅ 2Pc"M may be produced by template tetramerization.

[0057] While advantageous from enhanced thermal and chemical stability points of view, these new classes also form thin films on various surfaces. Such films exhibit physical and chemical properties that depend on the chemical composition of the phthalocyanine, including the ability to form intermolecular interactions that presumably would stabilize a derived materia! with long range order and superior coverage properties. Thus, materials that retain a high degree of fluorination and solubility in organic solvents, while exhibiting intermolecular interactions are desirable. Described herein is the production of exemplary new classes of such materials that exhibit π-π stacking interactions in solution and/or solid state.

[0058] Unlike the Fi6, F^Hs and FMPCMS, variants of the exemplary new classes exhibit asymmetric perfluorinated phthalocyanine molecules. FIG. 1 (b) illustrates exemplary general structures of asymmetric phthalocyanines. By asymmetry, it is meant that unlike the F]6, F24H8 and ?6 variants, the new classes do not exhibit four-fold axis of rotation. The resulting mirror plane geometry allows for increased solubility and the ability to form partial or total π- π stacking, as well as the advantageous properties of variability and tunability in aggregation, enhanced compatibility with polymers, variable film forming properties, variable optical properties, tunable magnetic and electronic interactions.

[0059] Turning now to FIG. 3, exemplary classes of molecules described herein are depicted. In particular, FIG. 3(a) shows a metallo-2,3,9, 10,16,17,23,24-octakis- (trifluoromethyl)-tetrafluorophthalocyanine, FisFLtPcM, FIG. 3(b) shows a metal lo-perf!uoro- 1 ,2,4-triisopropyl-phthalocyanine, F3 PcM, FIG. 3(c) shows a metallo-perffuoro- 1,2,4,8,10, 1 1 -hexa-isopropyl-phthalocyanine, F^Pc'M, FIG. 3(d) shows a metallo-perfluoro- 2,3,9,10-tetraisopropy!-phthalocyanine, F ₄ QPCM, and FIG. 3(e) shows a metallo-perfluoro- 2,3,9,10,16,17-hexaisopropyl-phthalocyanine, Fs2Pc"M. The asymmetric structure of the exemplary phthalocyanines, as discussed above with respect to FIG. 1(b), can be distinctly seen in FIG. 3.

[0060] The synthesis of all new F ₄ PcM, F ₄₀ PcM, F ₅ 2 c'M, and F ₅₂ Pc"M complexes has been accomplished by mixing the precursors P0, P2 and/or P3, taken in the appropriate ratios for the desired product with a metal salt, usually acetate. Precursor P0 is generally equivalent to tetrafluorophthalonitrile, as shown in FIG. 2(a), precursor P2 is generally equivalent to perfluoro-4,5-diisopropyl-phthalonitrile, as shown in FIG. 2(e), and precursor P3 is generally equivalent to perfluoro-3,5,6-triisopropyl phthalonitrile. Heating the mixtures using microwave radiation results in crude products that are subjected to chromatographic separations using silica gel and mixtures of acetone-hexanes with a progressively higher ratio of acetone (approximately 1 :10 to 10: 1 ). The yields vary depending on the particular product and whether the chromatography is repeated. Because the above procedure is generally applicable for all metals, the experimental models discussed herein are shown for illustrative purposes only and do not limit the scope of the disclosure.

[0061] Turning now to FIG. 4, F2sFLtPcM complexes are synthesized by the exemplary process depicted, with numbering of compounds. The present invention is not limited to the metals in the experimental exemplary embodiments. The products are best characterized by ^l9 F NMR, as well as by mass spectrometry. Single-crystal X-ray diffraction further provides both confirmation of compositional identity and also atomic-resolution of molecular and solid-state architectures. The compositional identity of the products is unambiguously established by mass spectrometry. [0062] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the present invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed.

EXAMPLE 1

[0063] In one exemplary embodiment, F28H4PCM is produced using the synthesis scheme described in FIG. 4 and the metal used is Zn. As will be apparent to one of ordinary skill in the art, the present exemplary embodiment embraces the use of multiple other metals as the synthesis scheme is not metal specific and would include, but not be limited to, other metals with ionic radii that would be coordinated by the four nitrogen atoms of the phthalocyanines, e.g., Co, Fe, Mg, Cu, and the like.

[0064] The exemplary synthesis scheme described in FIG. 4 includes Compounds 1 -12, which will be discussed in greater detail below.

Compounds 1 and 2

[0065] With reference to Compounds 1 and 2 of FIG. 4, an exemplary synthesis and characterization of l ,2-diiodo-4,5-dimethylbenzene (hereinafter "Compound 2") is depicted. In particular, a mixture of o-xylene (about 40.0 g, 0.377 mol), periodic acid (about 34.4 g, 0.151 mol) and iodine (about 84 g, 0.339 mol) is heated under stirring in a solution of acetic acid (about 200 mL), water (about 40 mL) and sulfuric acid 96% (about 6 mL) to approximately 70 °C for about 18 h. After cooling to about room temperature, the reaction mixture is poured over a solution of about 20 g Na2S2G ^" 3 in about 400 mL water, and about 300 mL CH2CI2 is added. Intense stirring for approximately five (5) minutes allows for the reduction of iodine. The organic phase is separated and the water phase is washed with CH2CI2 (about 2 x 150 mL). The combined organic layers are washed with a solution of about 15 g Na ₂ CC>3 in about 450 mL water (about 3 ^χ 150 mL), dried over MgS0 ₄ , filtered, evaporated in vacuo and recrystallized from methanol (about 700 mL) to afford white crystalline plates of Compound 2 in about 69% yield (about 83.4 g).

[0066] Specifically, the exemplary properties of Compound 2 are as follows: Mp: about

88-90 °C (taught by prior literature as 91 °C (see, e.g., Kovalenko, S. V. et al., Org. Lett.,

6(14), 2457 (2004))); Ή NMR (300 MHz, (CD ₃ ) ₂ CO): δ 2.17 (6H, s, CH ₃ ), 7.69 (2Η, s, Ph-

H); ¹³ C { ^! H} NMR (75 MHz, (CD ₃ ) ₂ CO) S 18.9, 104.2, 139.9, 140.8. Compound 3

[0067] With reference to Compound 3 of FIG. 4, an exemplary synthesis and characterization of ] ,2-bis(trifluoromethyl)-4,5-dimethylbenzene (hereinafter "Compound 3") is depicted. In particular, dry sodium trifluoroacetate (about 21 .8 g, 0.16 mol) and copper iodide (about 30.5 g, 0.16 mol) is mixed in about 150 mL dry NMP. To this suspension, a solution of Compound 2 (about 7.2 g, 0.02 mol) in about 50 mL dry NMP is added under stirring at approximately room temperature. The reaction mixture is then heated under nitrogen and kept at about 165 °C for about 22 h. Evolution of C0 ₂ may be monitored with an oil bubbler. After cooling, the mixture is poured into about 500 mL of hexanes, stirred intensively for about 30 min and allowed to settle. The upper hexane phase is filtered over silica gel, washed with water (about 3 ^χ 150 mL) and then dried over MgSC¼, filtered off and evaporated under reduced pressure until about 150 mL remain. This solution is further separated by flash chromatography with hexanes over silica gel. The product is collected as the top fraction. Careful removal of the solvent under a nitrogen stream followed by standing in the freezer for approximately 30 min allowed for separation of Compound 3 as colorless crystals in about 72% yield (about 3.5 g).

[0068] Specifically, the exemplary properties of Compound 3 are as follows: Mp: 38-39 °C (taught by prior literature as ranging from 38— 40 °C (see, e.g., Pawlowski, G. et al., Synthetic Communications, 1 1, 351 (1981 ) and Chambers, R. D. et al., Tetrahedron, 54, 4949, (1998))); ^f H NMR (300 MHz, CDC ): δ 2.37 (6H, s, C¾), 7.58 (2H, s, Ph-H); ¹⁹ F NMR (282 MHz, CDC1 ₃ ): δ -59.58 (6F, s, CF ₃ ).

Compound 4

[0069] With reference to Compound 4 of FIG. 4, an exemplary synthesis and characterization of l ,2-bis(trifluoromethyl)-3-nitro-4,5-dimethylbenzene (hereinafter "Compound 4") is depicted. In particular, a mixture of about 40 mL sulfuric acid about 96% (about 74 g, 750 mmol) and about 10 mL fuming nitric acid (about 15.2 g, 240 mmol) is given under stirring to Compound 3 (about 4.2 g, 17.2 mmol) and heated to approximately 60 °C for about 3 h. After cooling to about room temperature, the mixture is poured over about 300 g crushed ice. The milky solution is then extracted with CH2G2 (about 2 * 100 mL). The combined organic fractions are washed with about 3% a ₂ C0 ₃ solution (about 2 ^χ 150 mL) and then water (about 2 ^χ 200 mL). The CH2CI2 solution is dried over MgS0 ₄ , filtered and evaporated in vacuo. The crude yellowish solid is purified via silica gei filtration using hexanes to give white crystals of Compound 4 in about 90% yield (about 4.45 g).

[0070] Specifically, the exemplary properties of Compound 4 are as follows: p: 45^46 °C; I (KBr): 3075, 2924, 1620, 1554, 1453, 1380, 1319, 1278, 1 156, 1010, 952, 904, 768 cm ^"1 ; 'H NMR (300 MHz, (CD ₃ ) ₂ CO): δ 2.32 (3H, s, 5-CH ₃ ), 2.61 (3Η, s, 4-CH ₃ ), 8.10 ( 1 Η, s, Ph-H); ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -55.25 (3F, s, 2-C ₃ ), -57.85 (3F, s, 1-CFj); ^{l 3} C { ¹ H} NMR (75 MHz, (CD ₃ ) ₂ CO): δ 14.8 (s), 20.8 (s), 1 18.1 (q, J _C - _F = 35.0 Hz), 122.6 (q, Jc- _F = 274.5 Hz), 123.5 (q, J _C - _F = 273.4 Hz), 127.3 (q, J _C - _F = 33.8 Hz), 131.5 (q, J _C _ _F = 6.2 Hz), 135.4 (s), 147.3 (s), 151.2 (s); HRMS (EI): calcd. for [M] ⁺ (C ₁₀ H ₇ F ₆ NO ₂ ) ⁺ 287.0383 , found 287.0389.

[0071] With reference to FIG. 5(a), the X-ray structure of exemplary Compound 4 is illustrated with thermal ellipsoids set at about 50% probability.

Compound 5

[0072] With reference to Compound 5 of FIG. 4, an exemplary synthesis and characterization of l ,2-bis(trifluoromethyl)-3-fluoro-4,5-dimethylbenzene (hereinafter "Compound 5") is depicted. In particular, a solution of Compound 4 (about 2.1 g, 7.7 mmol) in about 25 mL dry DMF is added under stirring at approximately room temperature to a suspension of cesium fluoride (about 3.5 g, 24 mmol) in about 25 mL dry DMF. The mixture is heated under nitrogen to about 120 °C for about 70 h. After cooling, about 80 mL of water is added and the mixture is extracted with diethyl ether (about 3 ^x 100 mL). The ether fractions are joined, washed with water (about 3 x 100 mL), dried over MgS0 ₄ , filtered and then carefully evaporated in vacuo. The crude yellowish oil is purified via flash chromatography on silica gel using hexanes. Evaporation of the first eluted fraction, followed by standing for approximately 2 h at about—20 °C allows for the separation of Compound 5 as colorless crystals in about 34% yield (about 0.67 g). X-ray quality single crystals are obtained by slow evaporation of a refrigerated hexane solution.

[Θ073] Specifically, the exemplary properties of Compound 5 are as follows: Mp: 22-23 °C; Ή NMR (300 MHz, (CD ₃ ) ₂ CO): S 2.33 (3H, s, 5-C¾), 2.49 (3H, s, 4-CH ₃ ), 7.64 (1 Η, s, Ph-H); ^!9 F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -55.59 (3F, s, 2-C ₃ ), -57.85 (3F, s, 1 -G7¾ -1 12.18 (I F, m, Ph- ); { ^! H} NMR (75 MHz, (CD ₃ ) ₂ CO): S 1 1.2 (d, J _C _ _F = 6.9 Hz ), 20.0 (d, Jc-F = 2.6 Hz), 1 13.7 (q, J _C - _F = 34.1 Hz), 123.2 (q, J _C - _F = 273.2 Hz), 123.7 (qd, J _C _ _F = 272.6, 3.9 Hz), 125.1 (dq, J _C _ _F = 3.0, 6.7 Hz), 125.7 (q, J _C _ _F = 3 1 .8 Hz), 13 1.7 (d, J _c _ _F = 17.6 Hz), 146.3 (d, JoF = 6.4 Hz), 159.9 (dq, J _C - _F = 253.6, 2.5 Hz); HRMS (EI): calcd. for [M (C,oH ₇ F ₇ ) ⁺ 260.0436, found 260.0441.

[0074] With reference to FIG. 5(b), the X-ray structure of exemplary Compound 5 is illustrated with thermal ellipsoids set at about 50% probability.

Compound 6

[0075] With reference to Compound 6 of FIG. 4, an exemplary synthesis and characterization of 4,5-bis(trifluoromethyl)-3-fluoro-phthalic acid (hereinafter "Compound 6") is depicted. In particular, Compound 5 (about 1.2 g, 4.6 mmol) is dissolved in about 100 mL acetic acid glacial. To this solution, about 18 mL of sulfuric acid about 96% were added and the mixture is cooled to approximately 15 °C in an ice bath, under stirring. Chromium(VI) trioxide (about 2.1 g, 21 mmol) is added stepwise within approximately 30 min. After the addition, the ice bath is removed and the mixture is allowed to warm to approximately room temperature and then is heated to about 35 °C for about 20 h. Further, the mixture is diluted approximately 1.5 fold with water and about 15 mL methanol is added cautiously in order to destroy the excess Cr0 ₃ . The aqueous mixture is extracted with ethyl acetate (about 3 x 100 mL) and the combined organic fractions are washed with water (about 2 x 50 mL) and dried over MgSC . After filtration, the solvent is evaporated completely under vacuum and the crude yellow product is recrystallized from toluene (about 150 mL), separating Compound 6 as a white crystalline solid in about 53% yield (about 0.78 g).

[0076] Specifically, the exemplary properties of Compound 6 are as follows: Mp: 195- 196 °C; IR ( Br): 3600-2400, 3031 , 2668, 2593, 1729, 1495, 1419, 1281 , 1201 , 1 103, 989, 919, 737 cm ' ; Ή NMR (300 MHz, (CD ₃ ) ₂ CO): δ 8.36 (1H, s, Ph-H); ^S9 F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -56.08 (3F, s, 4-OF ₃ ), "58.44 (3F, s, 5-Ci¾ -1 1 1.36 (1 F, m, Ph- ); ^I3 C {Ή} NMR (75 MHz, (CD ₃ ) ₂ SO): S 118.4 (qd, J _C -P = 34.6, 14.2 Hz), 121.0 (q, J _C -F = 275.9 Hz), 121 .6 (qd, Jc-F = 274.2, 3.5 Hz), 124.7 (octet, J _C -F = 3.3 Hz), 127.9 (q, J _C -F = 34.6 Hz), 130.2 (d, J _C -F = 23.1 Hz), 134.7 (d, J _C -F = 5.5 Hz), 156.8 (d, J _C - _F = 258.1 Hz), 163.3 (s), 163.8 (s); HRMS (El): calcd. for [M] ⁺ (C _{l 0} H ₃ F ₇ O ₄ ) ⁺ 319.9920, found 319.9909.

[0077] With reference to FIG. 5(c), the X-ray structure for exemplary Compound 6 is illustrated with thermal ellipsoids set at about 50% probability. Compound 7

[0078] With reference to Compound 7 of FIG. 4, an exemplary synthesis and characterization of 4,5-bis(trifluoromethyl)-3-fluoro-phthalic anhydride (hereinafter "Compound 7") is depicted. In particular, about 0.58 g (about 1.8 mmol) of Compound 6 are suspended in about 2.5 mL (about 4.1 g, 34.5 mmol) thionyi chloride and heated to approximately 90 °C under stirring for about 3 h. After cooling to approximately room temperature, the excess thionyi chloride is evaporated under an air stream and the product is analyzed and used fresh for phthalimide production. As a result, white Compound 7 is obtained in about 92% yield (about 0.51 g).

[0079] Specifically, the exemplary properties of Solid 7 are as follows: Mp: 81-84 °C; IR (KBr): 3037, 1870, 1791, 1623, 1296, 1 162, 1 100, 910, 732 cm ^-1 ; Ή NMR (300 MHz, (CD ₃ ) ₂ CO): δ 8.56 (1H, s, Ph-H); ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -55.68 (3F, s, 4-GF ₃ ), -58.31 (3F, s, 5-GF ₃ ), -107.51 (IF, m, Ph- ). Extreme moisture sensitivity does not allow for well-resolved ¹ C NMR and satisfactory HRMS.

Compound 8

[0080] With reference to Compound 8 of FIG. 4, an exemplary synthesis and characterization of 4,5-bis(trifJuoromethyl)-3-fluorophthalimide (hereinafter "Compound 8") is depicted. In particular, about 0.5 g (about 1.66 mmol) of freshly obtained Compound 7 is mixed intensively with urea (about 0.2 g, 3.32 mmol) and heated under stirring to approximately 140 °C for about 2 h. The white solid product is analyzed and used as received for the next step. As a result, Compound 8 is obtained in about 95% yield (about 0.48 g).

[0081] Specifically, the exemplary properties of Compound 8 are as follows: Mp: 184— 186 °C; IR (KBr): 3453, 3360, 3251 , 3072, 2738, 1744, 1661 , 1624, 1329, 1282, 1 177, 993, 744, 654 cm ^"1 ; Ή NMR (300 MHz, (CD ₃ ) ₂ CO): δ 5.39 (1 H, br, NH), 8.21 (1 Η, s, Ph-H); ^,9 F NMR (282 MHz, (CD ₃ ) ₂ CO): S -55.57 (3F, s, 4-Ci¾ -58.11 (3F, s, 5-Ci¾ -1 1 1.33 (I F, m, Ph- ); HRMS (EI): ca!cd. for [M] ⁺ (C, ₀ H ₂ F ₇ NO ₂ ) ⁺ 300.9974, found 300.9975. Low solubility does not allow for a well-resolved ¹³ C NMR spectrum.

Compound 9

[0082] With reference to Compound 9 of FIG. 4, an exemplary synthesis and characterization of 4,5-bis(trifluoromethyl)-3-fluorophthalamide (hereinafter "Compound 9") is depicted. In particular, Compound 8 (about 0.48 g, 1 .58 mmol) is powdered, suspended in about 20 mL ammonium hydroxide about 28% and stirred for approximately 18 h. The mixture becomes a thick paste, which is filtered off and dried under vacuum to afford white Compound 9 in about 70% yield (about 0.35 g).

[0083] Specifically, the exemplary properties of Compound 9 are as follows: Mp: 203- 204 °C; IR (KBr): 3461 , 3422, 3305, 3025, 1713, 1610, 1356, 1 128, 766 cm ^"1 ; Ή NMR (300 MHz, (CD ₃ ) ₂ CO): δ 7.27 (IH, s, l -CONH ₂ ), 7.48 ( 1Η, s, 2-CON¾), 7.62 (1Η, s, l-CONH ₂ ), 7.74 (1 Η, s, 2-CONH ₂ 8.06 (1Η, s, Ph-H); ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): J -55.59 (3F, s, 4-C 3). -58.26 (3F, s, 5-GF3), -1 10.59 (I F, m, Ph- ); HRMS (EI): calcd. for [M] ⁺ (C ₁₀ H ₅ F ₇ N ₂ O2) ⁺ 318.0239, found 318.0232.

Compound 10

[0084] With reference to Compound 10 of FIG. 4, an exemplary synthesis and characterization of 4,5-bis(trifluoromethyl)-3-fluorophthalonitrile (hereinafter "Compound 10") is depicted. In particular, Compound 9 (about 0.1 g, 0.31 mmol) is dissolved in about 2 mL dry DMF. The solution is cooled to approximately—10 °C and a solution of about 72 μί, (about 0.12 g, 1 mmol) thiony] chloride in about 2 mL dry DMF is dropped within approximately 15 min. After stirring for about 30 min at approximately -10 °C, the mixture is allowed to warm to about room temperature and stirred overnight. The brownish solution is then given to about 50 g ice and stirred for approximately 15 min. The crude solid is filtered off, dried under air, re-dissolved in acetone and filtered again from brown impurities. Evaporation of the acetone solution gives a gray Compound 10 in about 52% yield (about 0.045 g).

[0085] Specifically, the exemplary properties of Compound 10 are as follows: Mp: 35- 36°C; IR (KBr): 3128, 3078, 2247, 1739, 1621 , 1573, 1430, 1343, 1 183, 1 120, 1014, 930, 684 cm ^" '; Ή NMR (300 MHz, (CD ₃ ) ₂ CO): 3 8.71 (IH, s, Ph-H); ^,9 F NMR (282 MHz, (CD ₃ ) ₂ CO): S ^~ 56.29 (3F, s, 4-CF ₃ ), -58.69 (3F, s, 5-CFj), -99.35 (IF, m, Ph-F); ¹³ C {Ή} NMR (75 MHz, (CD ₃ ) ₂ CO): δ 1 10.5 (s), 3 12.7 (d, J _C -F = 20.6 Hz), 1 13.9 (d, J _C - _F = 2.3 Hz), 121.4 (q, Jc-F = 275.9 Hz), 121 .8 (d, J _C - _F = 12-3 Hz), 122.0 (qd, JoF = 274.9, 3.3 Hz), 122.3 (s), 129.9 (dq, J _C -F = 4.5, 6.8 Hz), 134.3 (q, J _C -F = 34.8 Hz), 162.6 (dq, J _C _ _F = 270.0, 2.1 Hz); HRMS (EI): calcd. for [M] ⁺ (C, ₀ HF7N ₂ ) ⁺ 282.0028, found 282.0037.

[0086] With reference to FIG. 5(d), the X-ray structure of exemplary Compound 10 is illustrated with thermal ellipsoids set at about 50% probability. Compound 1 1

[0087] With reference to Compound 1 1 of FIG. 4, an exemplary synthesis and characterization of 2,3,9,10,16, 17,23,24-octakis-(trifluoromethyl)- tetrafluorophthalocyaninato-zinc(II) (hereinafter "Compound 1 1 ") is depicted. In particular, about 0.24 g (about 0.85 mmol) of Compound 10, about 0.08 g (about 0.43 mmol) zinc(II) acetate dihydrate and about 2 mL nitrobenzene are mixed in an approximately 10 mL glass reaction vessel, sealed with a Teflon cap and heated under microwave radiation for about 15 min at approximately 200 °C. After cooling down, the blue-green solid is dissolved in ethyl acetate and purified via flash chromatography on silica gel (mesh size approximately 35-70) using first ethyl acetate and then acetone/hexane (about 1 : 1) as eluents. Evaporation of the solvent affords dark blue Compound 1 1 in about 38% yield (about 0.096 g). X-ray quality single crystals are then obtained by slow evaporation of an acetone/acetonitrile (about 1 : 1) solution.

[0088] Specifically, the exemplary properties of Compound 1 1 are as follows: Mp > 300 °C; TGA: sublimes at 475 °C; UV-Vis (CHC1 ₃ ): _max (log ε) 675 (5.25), 647 (4.42), 609 (4.44), 378 (4.56) nm (L mol ¹ cm ^-1 ); IR ( JBr): 2928, 1633, 1414, 1285, 1 161 , 942, 720 cm Ή NMR (300 MHz, (CD ₃ ) ₂ CO): δ 9.1 1-9.46 (4H, m, Ph-H); ^l9 F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -53.48 ( 12F, br, CF ₃ ), -56.72 ( 12F, br, Ci¾ -109.09 (4F, br, P -F); HRMS (APCI+): calcd. for [M + H] ⁺ (C ₄₀ H _s F ₂₈ N ₈ Zn) ⁺ 1 192.9476, found 1 192.9491.

[0089] With reference to FIG. 6, the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F ₂₈ H ₄ PcZn are depicted, indicating the calculated value for [M + H] ⁺ .

[0090] Turning now to FIGS. 7(a)-(c), UV-Vis data comparison is displayed of partially aggregated F ₂₈ H PcZn with sterically non-hindered Fis cZn and sterically hindered Fe ₄ PcZn. It should be noted that the spectra of FIGS. 7(a)-(c) have been recorded in acetone. Further, the UV-Vis data for F ₂₈ H PcZn is displayed in FIG. 7(a), for FiePcZn in FIG. 7(b), and for Fe ₄ PcZn in FIG. 7(c).

[0091] With reference to FIGS. 8(a)-(d), UV-Vis electronic absorption spectra of F ₂₈ H PcZn are shown, depicting strong solvent-dependent aggregation. In particular, FIG. 8(a) illustrates a spectrum recorded in chloroform, in which F ₂₈ H ₄ PcZn is a monomer with minimal aggregation, FIG. 8(b) illustrates a spectrum recorded in ethyl acetate, in which F ₂₈ H ₄ PcZn is mostly a monomer, FIG. 8(c) illustrates a spectrum recorded in acetone, in which F ₂ gH ₄ PcZn displays intermediate aggregation, and FIG. 8(d) illustrates a spectrum recorded in ethanol, in which F ₂ gH ₄ PcZn is mostly aggregated.

[0092] Turning now to FIG. 9(a), X-ray structures of another exemplary embodiment of F2gH4PcZn(CH ₃ CN) are depicted showing metal-coordinated acetonitrile with H atoms omitted for clarity. The thermal ellipsoids are depicted at about 40% probability. It should be noted that the presence of the aromatic F at both non-peripheral positions in a non- equivalent ratio indicates the presence of at least two stereoisomers. While a statistical disorder about the ring plane may be less likely, it is not impossible. For clarity, FIG. 9(a) only illustrates the major population of F atoms on each ring. With reference to FIG. 9(b), it illustrates the top view of the π-π stacking region of two adjacent molecules of exemplary F28H4PcZn, with the darker atoms belonging to the upper molecule. FIG. 9(c) further illustrates a ball-and-stick representation of the side view of the aggregation of exemplary F2gH ₄ PcZn in a solid state.

Compound 12

[0093] With reference to Compound 12 of FIG. 4, an exemplary synthesis and characterization of 2,3,9,10,16,17,23,24-octakis-(trifluoromethyl)- tetrafluorophthalocyaninato-cobalt(II) (hereinafter "Compound 12") is depicted. In particular, Compound 12 is prepared and purified in a similar manner to Compound 1 1 , using about 0.035 g (about 0.12 mmol) of Compound 10, about 0.012 g (about 0.07 mmol) cobalt(II) acetate tetrahydrate and about 2 mL nitrobenzene. The brute blue-green solid obtained after evaporation of the ethyl acetate fraction is treated with about 50 mL acetone, filtered and dried under air to afford purple-violet Compound 12 in about 51 % yield (about 0.01 8 g).

[0094] Specifically, the exemplary properties of Compound 12 are as follows: Mp > 300 °C; UV-Vis (CHC1 ₃ ): ^ _max (log ε) 665 (4.56), 602 (3.92), 347 (4.24) nm (L mof ¹ cm ' ); ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -53.87 (12F, br, CF ₃ ), -56.72 (12F, br, CF ₃ ), - 108.94 (4F, br, Ph- ); HRMS (APCI+): calcd. for [M + H] ⁺ 1 187.9517, found 1 1 87.9564.

[0095] With reference to FIG. 10, the measured exact mass spectrum (positive ion APC1) and isotope pattern for [ + H] ⁺ for F2 ₈ H4PCC0 are depicted, indicating the calculated value for [M + H] ⁺ . EXAMPLE 2

[0096] With reference to FIG. 1 1 , an exemplary synthesis scheme for production of asymmetric F34PCM and F ₅ 2Pc'M is depicted, showing the results of the combination of precursors P0 and P3 and including Compounds 15, 16, 17 and 18, which will be discussed in greater detail below. It should be noted that the F34 CM and F ₅ 2pc'M compounds are obtained together. Further, the approximately 3:1 molecular tetramerization of the two precursors yields F34PCM compound, while the approximately 2:2 tetramerization yields F52Pc'M compound. As should be noted, the Pc' notation is used to differentiate two F 2PC compositionals (see, e.g., FIG. 3). In one experimental embodiment of this class of molecules the metal used is Zn. As will be apparent to one of ordinary skill in the art, the present embodiment embraces the use of multiple other metals as the synthesis scheme is not metal specific and would include, but not be limited to, other metals with ionic radii that would be coordinated by the four nitrogen atoms of the phthalocyanines, i.e., Co, Fe, Mg, Cu, and the like.

Compounds 15 and 16

[0097] With reference to Compounds 15 and 16, an exemplary synthesis and characterization of F34 cZn (hereinafter "Compound 15") and F5 ₂ Pc'Zn (hereinafter

"Compound 16") are depicted. In particular, twenty (20) thick walled glass reaction vessels

(about 10 mL volume) are charged each with about 0.4 g (about 0.62 mmol) perfluoro-3,5,6- triisopropyl phthalonitrile, (depicted in FIG. 1 1 as P3 and hereinafter "Compound 14"), about

0.04 g (about 0.2 mmol) tetrafluorophthalonitrile (depicted in FIG. 1 1 as P0 and hereinafter

"Compound 13") and about 0.04 g (about 0.22 mmol) zinc(II) acetate dihydrate. Then, catalytic amounts of ammonium molibdate, and about 1 mL nitrobenzene are added to each vial. The sealed vessels are heated in a microwave reactor at approximately 180 °C for about

1 min. The crude solid of each vial is extracted with about 50 mL ethyl acetate, the organic fractions are combined, concentrated in vacuo and adsorbed to silica gel (mesh size approximately 70-230). Gel filtration using an acetone/hexane approximately 2:98 mixture

(v/v) allows for the complete separation of nitrobenzene, unreacted Compound 14 and most yellowish impurities. The resulting blue-green solid is collected and subjected to column chromatography under gradually increasing solvent polarity. The rest of yellow impurities are removed with acetone/hexane approximately 2:98 mixture, followed by the separation of the green exemplary F5 ₂ Pc'Zn, eluted with an approximately 10:90 mixture, the royal blue exemplary F3 ₄ PcZn at approximately 20:80 polarity, and finally the dark blue exemplary Fi ₆ PcZn as a side product using an approximately 40:60 mixture (v/v). The three colored fractions are evaporated and re-purified by gel filtration on short columns, eluting with the corresponding mixtures used for their initial separation. Removal of the solvent and drying of the compounds allows for isolation of exemplary FsaPc'Zn in about 13% yield (about 0.42 g), exemplary T^PcZn in about 16% yield (about 0.26 g) and exemplary FigPcZn in about 14% yield (about 0.1 g), all based on starting material Compound 13.

[0098] Specifically, the exemplary properties for Compound 15, i.e., F3 ₄ PcZn, are as follows: Mp > 300 °C; UV-vis (CHC1 ₃ ): _max (log e) 689 (5.09), 672 (4.99), 632 (4.44), 614 (4.41), 365 (4.69) nm (L mol ¹ cm ¹ ); IR (KBr): 1522, 1489, 1383, 1282, 1236, 1 133, 964 cm ^"1 ; ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -69.05 (6F, br, CF ₃ ), -72.25 (12F, s, CF ₃ ), -97.12 (IF, s, Ar-F), -131.4 (IF, s, CF), -135.09 (I F, d, Ar-F), -139.18 to -141.66.(5F, m, Ar-F), -149.92 to -151.6 (6F, m, Ar-F), -161.39 (IF, d, CF), -165.99 to -170.18 (I F, m, CF); HRMS (APCI+): calcd. for [M + H] ⁺ (C ₄ iHF ₃ 4N ₈ Zn) ⁺ 1314.9067, found 1314.9080.

[0099] With reference to FIG. 12, the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F3 ₄ PcZn are depicted, indicating the calculated value for [M + H] ⁺ .

[00100] Turning now to FIGS. 13(a)-(b), the UV-Vis electronic absorption spectra of F3 ₄ PcZn are illustrated, showing solvent- dependent aggregation. In particular, FIG. 33(a) illustrates a spectrum recorded in chloroform, in which F3 ₄ PcZn is a monomer, and FIG. 13(b) illustrates a spectrum recorded in ethanol, in which F3 ₄ PcZn displays a significant degree of dimerization.

[00101] Further, the exemplary properties for Compound 16, i.e., F52Pc'Zn, are as follows: Mp > 300 °C; UV-vis (CHC1 ₃ ): X _mm (log ε) 701 (5.10), 674 (4.97), 640 (4.62), 615 (4.44), 372 (4.78) nm (L mol ^"1 cm ^"1 ); IR (KBr): 1523, 1489, 1375, 1287, 1236, 1 166, 1 127, 1050, 966, 939, 737 cnT ¹ ; ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -63.23 (3F, br, C¾ -68.52 (3F, br, CF ₃ ), -70.69 to -76.31 (30F, m, CF ), -97.56 (2F, br, Ar-F), -130.85 (I F, d, CF), -137.91 to -141 .55 (5F, m, Ar-F), -151.23 to -152.76 (4F, m, Ar-F), -161 .49 (I F, d, CF), -166.47 to -170.15 (3F, m, CF); HRMS (APCI+): calcd. for [M + H] ⁺ 1764.8780, found 1764.8804.

[00102] With reference to FIG. 14, the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ^÷ for F ₅ 2 c'Zn are depicted, indicating the calculated value for [00103] Turning now to FIG. 15, the X-ray structure of F ₅₂ Pc'Zn(OPPh ₃ ) is depicted, showing a metal-coordinated triphenyl phosphine oxide molecule. The thermal ellipsoids are plotted at about 35% probability and rotational disorder of the CF3 groups of -C3F7 is present, specifically shown as dashed lines.

[00104] With reference to FIG. 16, the side view of the aggregation in solid state of F52Pc'Zn is illustrated. In particular, the toluene molecules in the crystalline lattice and the atoms of coordinated triphenyl phosphine oxide, except oxygen, have been omitted. Further, the /-C3F7 groups are shown in ball-and-stick representation and the interplanar stacking distance, approximately 3.663 A, proves the existence of π-π interactions.

Compounds 17 and 18

[00105] With reference to Compounds 17 and 18, an exemplary synthesis and characterization of F ₃₄ PcCo (hereinafter "Compound 17") and F ₅₂ Pc'Co (hereinafter "Compound 18") is depicted. In particular, Compounds 17 and 18 are prepared similarly to Compounds 15 and 16, using sixteen (16) glass vessels, each charged with about 0.3 g (about 0.47 mmol) of Compound 14, about 0.05 g (about 0.25 mmol) of Compound 13 and about 0.045 g (about 0.18 mmol) cobalt(II) acetate tetrahydrate. Microwave heating is performed for approximately 12 min at about 185 °C. Initial purification of the brute solid by gel filtration is done with a toluene hexane approximately 1 :9 mixture (v/v). The rest of the separations are carried out as described for Compounds 1 and 16. Evaporation of the eluted fractions and drying to constant weight allows for isolation of green exemplary F5 ₂ Pc'Co (Compound 18) in about 1.5% yield (about 0.05 g), exemplary F ₃₄ PcCo (Compound 17) in about 1 1 % yield (about 0.19 g) and exemplary F _]6 PcCo as a side product in about 10% yield (about 0.084 g), based on starting material Compound 13. About 4.5 g of Compound 14 are recovered following the initial separation (about 90% of initial amount). X-ray quality single crystals for exemplary F ₃₄ PcCo are obtained by slow evaporation of an acetonitrile/toluene approximately 1 :1 solution.

[00106] Specifically, the exemplary properties of Compound 17, i.e., F3 ₄ PcCo, are as follows: Mp > 300 °C; UV-vis (CHCI ₃ ): l _mm (log e) 680 (4.52), 667 (4.50), 61 1 (4.03) nm (L moF ¹ cm ^-1 ); ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -63.58 (3F, br, GF ₃ ), -67.36 (3F, s, CF ₃ ), -68.75 to -76.79 (12F, m, CF ₃ ), -100.98 (I F, br, Ar-F), -132.36 (I F, s, CF), -137.64 (I F, d, Ar-F), -139.44 to -142.63 (5F, m, Ar-F), -155.92 to -157.62 (6F, m, Ar-F), -165.55 (I F, d, CF), -169.46 (IF, br, CF); HRMS (APCI-): calcd. for [M] ^~ (C41F ₃ 4N8C0) 1308.9040, found 1308.9032.

[00107] With reference to FIG. 17, the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M] ^~ for F ₃ 4PCC0 are depicted, indicating the calculated value for [M] ^~ .

[00108] Turning now to FIG. 18(a), the side view of the aggregation in solid state of F ₃ 4PCC0 is illustrated. In particular, the toluene molecules in the crystalline lattice and the H atoms of coordinated acetonitrile have been omitted and the Z-C ₃ F7 groups are depicted as van der Waals spheres. The interplanar stacking distance, approximately 3.25 A, illustrates the existence of π-π interactions. With reference to FIG. 18(b), a top view of the π-π stacking region of two adjacent molecules of F ₃ 4PCC0 is depicted.

[00109] With reference to FIG. 19, the X-ray structure of F3 ₄ PcCo(CH ₃ CN) is depicted, showing a metal-coordinated acetonitrile molecule. In particular, the thermal ellipsoids are plotted at about 40% probability and rotational disorder of the CF3 groups of -C3F7 is present, as is shown by the dashed lines.

[00110] Further, the exemplary properties of Compound 18, i.e., Fs ₂ Pc'Co, are as follows: Mp > 300 °C; UV-vis (CHC1 ₃ ): _max (log e) 686 (4.62), 615 (4.1 8), 334 (4.58) nm (L mol ^{"1 ■} cm ^"1 ); ^l9 F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -63.62 (3F, br, C7¾, -67.01 to -76.28 (33F, m, CF ₃ ), -90.0 to -1 10.0 (2F, br, Ar-F), -137.5 to -147.5 (6F, m, Ar-F), -155.0 to - 1 59.5 (4F, br, Ar-F), -165.82 (I F, m, CF), -169.76 to -171.73 (3F, m, CF); HRMS (APC1-): calcd. for [M] ^~ (C ₅ oF ₅ 2NgCor 1758.8753, found 1758.8763.

[00111] With reference to FIG. 20, the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M] ^~ for F5 ₂ Pc'Co are depicted, indicating the calculated value for [Mf.

[00112] Turning now to FIG. 21 (a), a ball-and-stick representation of

F ₃₄ PcZn(H ₂ 0)*((CH ₃ ) ₂ CO) ₂ is depicted showing H-bonding between the H atoms of H ₂ 0 and the oxygen atoms (0 ₂ ) of the two acetone molecules. FIG. 21(b) is a van der Waals representation of the exemplary F ₃ PcZn(H ₂ 0)*((CH ₃ ) ₂ CO ₂ . FIG. 21(c) illustrates the side view of the aggregation in solid state of exemplary p ₃ 4PcZn. The acetone molecules in the crystalline lattice and the H atoms of coordinated H ₂ O have been omitted for clarity. The i-

C ₃ F7 groups are depicted as van der Waals spheres. The interplanar stacking distance, about

3.393 A, demonstrates the existence of π-π interactions. Further, FIG. 21 (d) illustrates a top view of the π-π stacking region of two adjacent molecules of exemplary F34PCZ11. [0ΘΠ3] Turning now to FIG. 22, the X-ray structure of F ₃ Pc2n(H ₂ 0) is illustrated, showing a metal -coordinated water molecule. In particular, the acetone molecules in the crystalline lattice have been omitted. The thermal ellipsoids of FIG. 22 are plotted at about 40% probability.

EXAMPLE 3

[00114] With reference to FIG. 23, an exemplary synthesis scheme for production of asymmetric F4 ₀ PCM and Fs2Pc"M is depicted, showing the results of the combination of precursors P0 and P2 and including Compounds 20, 21, 22 and 23, which will be discussed in greater detail below. It should be noted that the F ₄₀ PcM and F ₅₂ Pc"M compounds are obtained together. Further, the approximately 2:2 molecular tetramerization of the two precursors yields a F40PCM compound, while the approximately 1 :3 tetramerization yields a F52Pc"M compound. It should be noted that the Pc" notation is used to differentiate the two F52PC compositional isomers (see, e.g., FIG. 3). in one experimental embodiment of this class of molecules the metal used is Co. As would be apparent to one of ordinary skill in the art, the present embodiment embraces the use of multiple other metals as the synthesis scheme is not metal specific and would include, but not be limited to, other metals with ionic radii that would be coordinated by the four nitrogen atoms of the phthalocyanines, e.g., Zn, Fe, Mg, Cu, and the like.

Compounds 20 and 21

[00115] With reference to Compounds 20 and 21, an exemplary synthesis and characterization of F ₄ oPcZn (hereinafter "Compound 20") and F5 ₂ Pc"Zn (hereinafter "Compound 21") is depicted. In particular, about twenty-five (25) 10 mL glass reaction vessels are charged each with about 0.4 g (about 0.79 mmol) perfluoro-4,5-diisopropyi phthalonitrile (depicted in FIG. 23 as P2 and hereinafter "Compound 1 "), about 0.05 g (0.2 mmol) tetraftuorophthalonitrile (depicted in FIG. 23 as P0 and hereinafter "Compound 13") and about 0.03 g (about 0.19 mmol) zinc(II) acetate dihydrate. After the addition of catalytic amounts of ammonium molibdate and about 1 mL nitrobenzene in each vessel, the vessels are sealed and heated in a microwave reactor at approximately 185 °C for about 12 min. The crude solid of each vial is extracted with about 25 mL ethyl acetate, the organic fractions are combined, concentrated in vacuo and adsorbed to silica gel (mesh size approximately 70- 230). Chromatographic separation of the products is performed using neat hexane and then acetone/hexane approximately 2:98 mixture (v/v), which allows for complete removal of nitrobenzene, unreacted Compound 19 and yellowish impurities. Then, a blue fraction consisting of exemplary F _$ PcZn as a side product is eluted with an acetone/hexane approximately 1 :9 mixture, followed by a greenish-blue exemplary F5 ₂ Pc"Zn fraction (impurified with exemplary F6 ₄ PcZn). Finally, exemplary F ₄ oPcZn is eluted with an acetone/hexane approximately 2:8 mixture. Removal of the solvent under reduced pressure and re-purification of the products by gel filtration, evaporation and drying to constant weight allows for isolation of exemplary F ₅ 2Pc"Zn in about 25% yield (about 2.8 g) based on Compound 13, exemplary F ₄ oPcZn in about 22% yield (about 1.1 g) based on Compound 13 and exemplary F6 ₄ PcZn in about 31 % yield (about 3.2 g) based on Compound 19.

[00116] Specifically, the exemplary properties of Compound 20, i.e., F ₄ oPcZn, are as follows: Mp > 300 °C; UV-vis (CHCb): _max (log έ) 692 (5.24), 683 (5.23), 662 (4.80), 619 (4.67), 372 (4.84) nm (L mol ^"1 cm ^"1 ); IR (KBr): 1522, 1489, 1456, 1283, 1250, 1 170, 1 149, 1099, 965, 730 cm ^"1 ; ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -73.56 (24F, s, Ci¾ -103.85 (4F, br, Ar-F), -137.46 to -140.21 (4F, m, Ar- ), -149.56 to -150.85 (4F, m, r-F), -164.33 to -166.06 (4F, m, CF); HRMS (APCI+): calcd. for [M + H] ⁺ (C ₄₄ HF ₄₀ N ₈ Zn) ⁺ 1464.8971, found 1464.8965.

[00117] With reference to FIG. 24, the measured exact mass spectrum (positive ion APC1) and isotope pattern of [M + H] ⁺ for F ₄ oPcZn are depicted, indicating the calculated value for [M + H] ⁺ .

[00118] Turning now to FIG. 25, the X-ray structure of F ₄ oPcZn(OPPIi ₃ ) is illustrated as a ball-and-stick representation, showing metal-coordinated triphenyl phosphine oxide with H atoms omitted.

[00119] With reference to FIG. 26(a), the side view of the aggregation in solid state of F oPcZn(OPPli ₃ ) is depicted, showing metal-coordinated triphenyl phosphine oxide. In particular, the toluene and chloroform molecules in the crystalline lattice have been omitted and the interplanar stacking distance, approximately 3.264 A, demonstrates the existence of π-π interactions. With respect to FIG. 26(b), a top-down view of the π-π stacking region of two adjacent molecules of F ₄ oPcZn is illustrated. The F atoms of the -C ₃ F7 groups of the top molecule and the Zn atoms are specifically depicted as van der Waals spheres.

[00120] With reference to FIGS. 27(a)-(b), the UV-Vis electronic absorption spectra of F ₄ oPcZn are depicted, showing solvent-dependent aggregation. In particular, FIG. 27(a) illustrates a spectrum recorded in chloroform, in which F ₄ oPcZn is a monomer, and FIG. 27(b) illustrates a spectrum recorded in ethanol, in which F^PcZn displays strong aggregation.

[00121] Further, the exemplary properties of Compound 21 , i.e., F ₅ 2Pc"Zn, are as follows: Mp > 300°C; UV-vis (CHC1 ₃ ): _max (log ε) 689 (5.00), 675 (4.97), 613 (4.34), 375 (4.50) nm (L mol ^-1 cm ^"1 ); HRMS (APCI+): calcd. for [M + H] ⁺ (C5oHF _s2 N ₈ Zn) ⁺ 1764.8780, found 1764.8749.

[00122] With reference to FIG. 28, the measured exact mass spectrum (positive ion APCI) and isotope pattern of [M + H] ⁺ for F ₅ 2Pc"Zn are depicted, indicating the calculated value for [M + H] ⁺ .

Compounds 22 and 23

[00123] With reference to Compounds 22 and 23, an exemplary synthesis and characterization of F4 ₀ PCC0 (hereinafter "Compound 22") and F ₅₂ Pc"Co (hereinafter "Compound 23") is depicted. In particular, Compounds 22 and 23 are prepared similarly to Compounds 20 and 21 , using ten (10) glass vessels, each charged with about 0.4 g (about 0.79 mmol) of Compound 19, about 0.05 g (about 0.25 mmol) of Compound 13 and about 0.05 g (about 0.19 mmol) cobalt(II) acetate tetrahydrate. Removal of nitrobenzene and unreacted precursor Compound 19 is performed by flash chromatography with hexane and then toluene/hexane approximately 1 : 1 mixture (v/v). Exemplary F ₆₄ CC0 (side product) is eluted first, with an acetone/hexane approximately 1 : 10 mixture, followed by royal blue exemplary F ₄₀ PcCo (acetone/hexane 1 :5) and finally dark green exemplary F52Pc"Co, eluted with neat acetone. Repurification of Compounds 22 and 23 by flash chromatography with acetone/hexane mixtures of gradually increasing polarity, followed by evaporation of the collected fractions and drying to constant weight allows for the isolation of exemplary F ₄ oPcCo (Compound 22) in about 1 1% yield (about 0.22 g) and exemplary Fs2Pc"Co (Compound 23) in about 0.3% yield (about 0.01 g), based on Compound 13. Exemplary F6 ₄ PcCo is isolated as a side product in about 18% yield (about 0.73 g) based on Compound 19. X-ray quality single crystals of exemplary F ₄ oPcCo are obtained by slow evaporation of an acetone solution.

[00124] Specifically, the exemplary properties of Compound 22, i.e., F ₄ oPcCo, are as follows: Mp > 300°C; UV-vis (CHC1 ₃ ): (log ε) 672 (4.88), 607 (4.28), 352 (4.50) nm (L mol ^"1 cm ^-1 ); IR (KBr): 1528, 1480, 1251 , 1 170, 1 104, 964, 730 cm ^"1 ; ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): 5 -71 .38 (24F, s, CF ₃ ), -104.56 (4F, br, Ar-F), -141.0 to -144.0 (4F, br, Ar-F), -154.0 to -158.0 (4F, br, Ar-F), -165.18 (4F, s, CF); HRMS (ESI+): calcd. for [M + H] ⁺ (C ₄₄ HF ₄₀ N ₈ Co) ⁺ 1458.8934, found 1458.8897.

[00125] With reference to FIG. 29, the measured exact mass spectrum (positive ion ESI) and isotope pattern of [M + H] ⁺ for F ₄ QPCCO are depicted, indicating the calculated value for [M + H] ⁺ .

[Θ0126] Turning now to FIG. 30, the X-ray structure of F ₄ oPcCo(H ₂ 0) is illustrated, showing metal-coordinated water and acetone molecules in the lattice. It should be noted that the thermal ellipsoids depicted are plotted at about 40% probability.

[00127] Further, the exemplary properties of Compound 23, i.e., Fs ₂ Pc"Co, are as follows: Mp > 300°C; UV-vis (CHC1 ₃ ): _max (log ε) 674 (3.94), 641 (3.86), 442 (3.85), 417 (3.84) nm (L mof ¹ cirf ^! ); ¹⁹ F NMR (282 MHz, (CD ₃ ) ₂ CO): δ -71.57 (36F, s, Ci¾, -105.39 (6F, br, Ar-F), -137.0 to -143.0 (2F, br, Ax-F), -148.0 to -155.0 (2F, br, Ar-F), -165.17 (6F, s, CF); HRMS (APCI-): calcd. for [Mf (C ₅₀ F ₅₂ N ₈ Co) ^" 1758.8753, found 1758.8755.

[00128] With reference to FIG. 31, the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M] ^~ for F ₅₂ Pc"Co are depicted, indicating the calculated value for [Mf.

[00129] Turning now to FIGS. 32(a)-(b), the UV-vis electronic absorption spectra of Fs2Pc"Co is depicted, showing solvent-dependent aggregation. In particular, FIG. 32(a) illustrates a spectrum recorded in chloroform, in which F5 ₂ Pc"Co is slightly aggregated, and FIG. 32(b) illustrates a spectrum recorded in tetrahydrofuran, in which F5 ₂ Pc"Co shows an increased degree of aggregation.

CATALYTIC DRIVEN PATHWAY FOR OXIDIZING THIOLS

[00130] In accordance with embodiments of the present disclosure, novel catalytic driven pathways for oxidizing thiols are provided. In particular, the catalytic driven pathway for oxidizing thiols includes an iso-perfluoropropyl phthalocyanine catalyst and a redox reaction discussed with respect to Equations 1 (a) and 1(b) below. The iso-perfluoropropyl phthalocyanine is generally F6 ₄ PcM and provides advantageous properties, including at least one of enhanced Pc solubility, production of X-ray quality crystals of a halogenated Pc, and depression of Pc frontier orbitals.

[00131] Organic-based molecules are problematic for aerobic oxidations since their C-H bonds are susceptible to radical attack. With reference to FiG. 33(a), a general structure of exemplary cobait phthalocyanines is illustrated. In particular, FIG. 33(a) illustrates compounds H ₁₍ ;PcCo (hereinafter "1 -Co"), wherein Rj = R ₂ = H, FiePcCo (hereinafter "2- Co"), wherein R, = R ₂ = F, and F ₆₄ PcCo (hereinafter "3-Co"), wherein R, = -C3F7, R ₂ = F. FIG. 33(b) illustrates F ₆ PcCo(0 ₂ ) reaction intermediates, wherein 0 ₂ stands for both 0 ₂ ^~ and 0 ₂ ^2_ , drawn based on the X-ray structure of F64PcCo*((CH ₃ ) ₂ CO) ₂ with the F groups shown as van der Waals spheres and the Co coordination sphere depicted as balls-and-sticks. It should be noted that the atomic coordinates of all atoms, except 0 ₂ , have been determined experimentally.

[00132] Still with reference to FIG. 33, in the case of metal phthalocyanines, e.g., HigPcM (1-M), Cythochrome P450 related molecules, their C-H bonds and π-π stacking limit their utility as oxidation catalysts. The replacement of H by F to give FiePcM (2-M) generally enhances Pc stability, eliminates electrophilic degradation, but favors nucleophilic susceptibility (see, e.g., Leznoff, C. C. et al., Chem. Comm., 338, (2004)) while promoting aggregation. Thus, even the strongest C-X bonds are typically insufficient to render this class of advantageous molecules completely stable. Replacing half of the F atoms of 2-M with wo-perfluoropropyl ( -C ₃ F7) groups gives (i-C3Fv)sFgPcM, abbreviated as F ₆ 4pcM (3- M), which results in advantageous properties, e.g., enhances Pc solubility, produces the first X-ray quality crystals of a halogenated Pc and depresses the Pc frontier orbitals (see, e.g., Bench, B. A. et al., Angew. Chem. Int. Ed., 41 , 747 (2002), Bench, B. A. et al, Angew. Chem. Int. Ed., 41 , 750 (2002); a«<f Keizer, S. P. et al., J. Am. Chem. Soc, 125, 7067 (2003)). For 3-M, π-π stacking is disfavored both in solution and in the solid-state (see, e.g., Gerdes, R. et al, Dalton Trans., 1098 (2009) and Moons, H. et al, Inorg. Chem., 49, 8779 (2010)). Diamagnetic 3-Zn catalyzes the transfer of solar energy to ³ 0 ₂ to form Ό ₂ that oxygenates quantitatively an external substrate, (S)-(-)-citronellol (see, e.g., Keil, C. et al., Thin Solid Films, 517, 4379 (2009)).

[00133] Radical chemistry represents a challenge, which has been approached by examining a model reaction by the catalyzed autooxidation of corrosive and foul smelling RSH, a process generally practiced industrially (MEROX), catalyzed by partly sulfonated 1 - Co (see, e.g., Basu, B. et al., Catal. Rev., 35, 571 (1993)). The overall reaction stoichiometry may be shown by 4 RSH + 0 ₂ → 2 RSSR + 2 H ₂ 0. Redox reaction pathways, via both Co(Il)/Co(IIi) and Co(II)/Co(I) pairs are generally possible. In both cases S- and O-centered radicals are intermediates. For the relevant Co(II)/Co(I) pathway, shown below, the coordination of RS ^_ to Co(II) is followed by (i) the reduction of Co(II) to Co(l) and formation of RS*, (ii) oxidation of Co(I) by coordinated 0 ₂ to regenerate Co(II) and form 0 ₂ ^*~ , i.e., superoxide. The cycle may be repeated to form 0 ₂ ^2_ , i.e., peroxide, and RS* (see, e.g., Leung, P.-S. K. et al., J. Phys. Chem., 93, 430 (1989), Navid, A. et al., J. Porphyrins Phthalocyaninees, 3, 654 (1999), Schneider, G. et al., Photochem. Photobiol, 60, 333 (1994) and van Welzen, J. et al., Makromol. Chem., 190, 2477 (1989)). Reaction details may be shown in Equations 1(a) and 1 (b):

RS + PcCo(lI)→ [RS— Co(lI)Pc]→ [RS ^» — Co(I)Pc] ( 1 (a))

[RS ^« — Co(I)Pc]→ RS ^» + PcCo(II) + e ^" (1 (b))

[00134] Soluble (S0 ₃ H, S0 ₃ Na) ₄ PcCo, and (COOH) _2A8 PcCo (see, e.g., Shirai, H. et al., J. Phys. Chem., 95, 417 ( 1991 ) and Tyapochkin, E. M. et al., J. Porphyrins Phthalocyanines, 5, 405 (2001)) have been used to reveal mechanistic details in solution. Heterogenized systems used 1-Co, (COOH) ₄ PcCo, (N0 ₂ ) ₄ PcCo (see, e.g., Fischer, H. et al., Langmmr, 8, 2720 (1992)), (NH ₂ ) ₄ PcCo (see, e.g., Buck, T. et al., J. Mol. Catal, 70, 259 (1991)), (S0 ₃ Na) _]j2 PcCo (see, e.g., Leitao, A. et al., Chem. Eng. ScL, 44, 1245 (1989)), and (S0 ₃ ^~ ) ₄ PcCo (see, e.g., Chatti, I. et al., Catal. Today, 75, 1 13 (2002)). Polymer composites have also been used (see, e.g., van Welzen, J. et al., Makromol. Chem., 188, 1923 (1987) and van Welzen, J. et al., Makromol. Chem., 189, 587 (1988)). From a steric point of view, site- isolation in a matrix hinders the reaction of PcCo0 ₂ with another PcCo to form an inert μ- peroxo complex (see, e.g., Schutten, G. H. et al, Makromol. Chem., 180, 2341 (1979)). Turnover numbers generally increase, for example, for CioEbjSH from about 150 to about 770 (see, e.g., Perez-Bernal, M. E. et al., Catal. Lett., 1 1 , 55 (1991)). From an electronic point of view, since the Co(Il) to Co(I) reduction is the rate determining step (r.d.s.), stabilization of Co(I) is desired. Overstabilization, however, could hinder catalyst reoxidation to Co(II), as depicted by Equation 1(b), and thus the catalytic process. Indeed, a Sabatier (volcano) plot of the rate of electrocatalytic oxidation of RSH vs. the PcCo(II)/Co(I) reduction potentials exhibits a negative slope, indicating that the reoxidation to Co(II) generally controls the r.d.s. (see, e.g., Zagal, J. H. et al., Coord. Chem. Rev., 254, 2755 (2010) and Bedioui, F. et al., Phys. Chem. Chem. Phys., 9, 3383 (2007)). The potentials, in turn, correlate with substituents' Hammett constants, as illustrated in FIG. 34(a).

[00135] In particular, FIG. 34(a) displays a plot of Pc(Co(Il)/Co(l» reduction potentials vs. the sum of substituents' Hammett σ constants, wherein the following notation should be utilized: (S0 ₃ ^~ ) ₄ Pc: R, = SO , H; (NH ₂ ) ₄ Pc: R, = NH ₂ , H; (N0 ₂ ) ₄ Pc: R, = N0 ₂ , H; (OCH ₃ ) ₈ Pc: R| = OCH ₃ ; and (OC ₈ Hi ₇ ) ₄ Pc: R _t = OC _s H _{! 7} , H (see, e.g., Zagal, J. H. et al., Coord. Chem. Rev., 254, 2755 (2010)). Further, the equation for the distribution may be depicted as y = -0.579 + 0.0518x, wherein the correlation coefficient is approximately 0.9955. With reference to the inset figure of FIG. 34(a), the calculated reduction potentials for hypothetical (R^sFgPc, using R _f substituents with known Hammett constants, are illustrated (see, e.g., Hansch, C. et al., Chem. Rev., 91 , 165 (1991)). Still with reference to the inset figure, the following notations should be utilized: R ₂ = F and Ri = R _f in ascending order of the £°'co(n _/ » potentials, i.e., propyl, isopropyl (F6 ₄ Pc, experimental point), ethyl, methyl, and t-butyl. Turning now to FIG. 34(b), the 0 ₂ consumption in the catalyzed autooxidation of 2-mercaptoethanol in aqueous tetrahydrofuran is illustrated.

[00136] Previously, 2-Co was the extreme low-rate point due to the strongest F-induced stabilization of Co(I). The paramagnetic 3-Co, of certain exemplary embodiments of the present invention, may be electronically related to other PcCos, the majority exhibiting a singly occupied d _z ² and equivalent d _xz and d _yz orbitals (ESR in solution and solid-state, Table 1). Axial binding by the weakly coordinating acetone should be noted in solid-state. Coordination of N-methyl imidazole (ESR, FIGS. 35(a)-(b)) and ligand-independent site- isolation, e.g., for M = Zn (see, e.g., Gerdes, R. et al., Dalton Trans., 1098 (2009)), and Cu (see, e.g., Moons, H. et al., Inorg. Chem., 49, 8779 (2010)), in solution and in films (see, e.g., Keil, C. et al., Thin Solid Films, 517, 4379 (2009)) are characteristics imparted by the F64PC scaffold. The thennal stability of 3-Co is generally high and the complex sublimes in air at approximately 380 °C without decomposition. Interestingly, 3-Co cannot be electrochemically oxidized to Co(III) in DMF, but its reduction occurs at approximately £°' = -0.22 V (vs. SCE), thus justifying the choice of the Co(II)/Co(I) catalytic pathway for certain embodiments of the present invention. Further, the Zn reduction value is about -0.30 V (see, e.g., Bench, B. A,, Ph.D. Dissertation, Brown University (2001 )).

TABLE 1 : ESR parameters of selected phthalocyanines

Complex g± gll Reference

H ₁₆ PcCo, Cariati, F. et al., J. Chem. Soc, Dalton Trans., 556

2.60 1.99

in acetone (3975)

F ₆₄ PcCo,

2.276 2.0026 Loas, A. et al., Dalton Trans., 40, 5162 (201 1) in acetone

F ₆ 4PCC0,

2.282 2.0063 Loas, A. et al., Dalton Trans., 40, 5162 (201 1 ) powder

(S0 ₃ H) ₄ PcCo,

2.26 2.006 Zwart, J. et al, J. Mol Catal 5, 51 (1979) in DMF [00137] A statistical X-ray analysis of all Co porphyrins (Por) and Pes in the Cambridge Crystallographic Database (see, e.g., Allen, F. H., Acta Crystaltogr. Sect. B, 58, 380 (2002)) indicates that Co deviates by less than about 0.1 A from the ligand N ₄ coordination plane regardless of its oxidation state (I, II or III) or coordination number. For Pes, the mean Co-N distances differ by approximately 1 e.s.d. when Co(II) and Co(III) are considered, i.e., approximately a 1 .927±0.003 A average. For the only PcCo(I) complex, the Co-N distances range is approximately 1 .879-1.914 A with a mean of about 1.896 A (see, e.g., Huckstadt, H. et al., Z. Anorg. Allg. Chem., 624, 715 (1998)). The shortening of the Co-N distances upon reduction from Co(II) to Co(I), i.e., about 0.035 A, is generally identical for both Por's and Pc's. It should be noted that the mean Co(II)-N distance in 3-Co, i.e., about 1 .926 A, is typical for both Co(ll) and Co(III) and thus Co(I) is not favored.

[00138] Taken together, the X-ray data suggests neither a structural hindrance for oxidation of Co(II) to Co(III), nor a preference for the reduction of Co(II) to Co(I). Thus, the 3-Co's record electronic deficiency, as shown in FIG. 34(a), beyond 2-Co, is determined by electronic factors, e.g., aromatic F replacement by Rf groups exacerbates electronic deficiency due to loss of aromatic F π-back bonding. Relevant for catalysis, as illustrated by Equation 1 (a) above, the reversible chemical reduction 3-Co(II) <→ 3-Co(I) occurs in the presence of HO ions, as indicated by isosbestic points and the increase of the approximately 710 nm Q-band of the Co(l) complex at the expense of the approximately 670 nm Q-band of the Co(II) one (see FIG. 36). Further, addition of HC1 completely reverses the reduction. In contrast, the isostructural Fe ₄ Pc(2-)Zn(II) «→ F ₆ 4Pc(3-)Zn(II) reduction is l igand centered. The actual catalytic activity of 3-Co is far from certain given (i) the inverse correlation between electron deficiency and thiol oxidation rates, (ii) strong S^Co bonds, a soft-soft type interaction and (iii) a high affinity for axial ligands. Thus, DFT frontier orbital energies calculations for 1-Co, 2-Co and (CzFsJgFgPcCo (F ₄ gPcCo, 3'-Co) a surrogate for 3-Co, which is too large for the calculations, reveal that the ionization potentials increase by approximately 1 .3 eV and approximately 1.1 eV from 1 -Co to 2-Co and 2-Co to 3 '-Co, respectively. Since C2F5 and /-C3F7 have similar Hammett constants (see, e.g., Hansch, C. et al ., Chem. Rev., 91, 165 ( 1991 )), illustrated by the inset of FIG. 34(a), 3-Co and 3 '-Co should have similar potentials. Electron affinity varies similarly, establishing progressively more difficult oxidation/easier reduction and more favorable axial binding as the F content increases. [00139] Turning now to FIG. 34(b), the results of thiol coupling using 1-, 2- and 3-Co and 2-mercaptoethanoi (hereinafter "2 -ME") are shown, in particular, the reactions produce only the expected 2-hydroxyethyI disulfide (identified by Ή and ^I3 C NMR). No other S-oxidized products are observed, thus allowing an approximately 4:1 direct correlation between the number of moles of thiol and (¾ consumed, respectively. In the presence of about a 1000 fold molar excess of thiol, but in the absence of a base, 3-Co(II) is generally not reduced. In contrast, the formation of the thiolate ion upon addition of NaOH, [thiol]/[NaOH] = approximately 1 10/1 , results in instantaneous appearance of 3-Co(I) (as demonstrated by UV- Vis, FIG. 36). Immediate 0 ₂ uptake occurs only when both RS ^~ and the catalyst are present. It is noted that light makes no difference indicating absence of solar energy transfer. With reference to Table 2, the catalysis parameters are listed below:

TABLE 2: Parameters of the catalyzed autooxidation of 2-mercaptoethanol

Catalyst Stability" Rate ^b TOF ^c TON ^d

HiePcCo 75% 23.8 3.0 12,600

F| ₆ PcCo 35% 4.9 0.84 7,700

F^PcCo >99% 12.8 1.74 13,000

² Stability is defined as the ration of (Q-band intensities after 24 hours/initial intensities) x 100. See also FIGS. 38(a)-(c). Pc degradation products have not been identified.

Initial reaction rate, i.e., μηιοί 0 ₂ min ^" ', calculated from the linear fit portion of FIG. 34(a).

c Turnover frequency, i.e., RSH sec ^" ' mol Pc ^"1 , calculated under pseudo-first order conditions.

d Total oxidation number after 5 hours, limited by the RSH batch reaction to approximately 13,000.

[Θ0140] 3-Co is highly stable at about 25 °C under the reaction conditions with nucleophiles and radicals present. Moreover, 3-Co showed no degradation for at least two (2) days in refluxing, basic aqueous tetrahydrofuran, or concentrated H2SO4. Since the aromatic F substituents in 3-Co should generally be more susceptible to nucleophilic attack relative to 2 -Co, the protective steric effect imparted by the /-C3F7 groups becomes apparent.

[00141] The initial oxidation rates are partly incongruent with the reduction potentials. In particular, the calculated ratio of initial reaction rates for 2-Co/l-Co based on reduction potentials is about 0.16 vs. the observed value of about 0.84/3.0 = 0.28. In contrast, 3-Co, presumably less efficient than 2-Co, has a rate approximately twice as high, about 20 times faster than predicted based on reduction potentials. Since the reoxidation of Co(I) to Co(H) (the r.d.s.) proceeded as expected based on free energy correlations, the discrepancy is unexplainable on electronic grounds alone. Potential reasons for the enhanced rate of 3-Co includes: (i) R steric crowding leading to an accelerated departure of the thyil radical (product), a classical feature of enzymatic reactions and consistent with the limited miscibility of hydrocarbons and fluorinated solvents, (ii) an R _f -induced extra loss of Co ²⁺ polarizability, making it unlikely to bind soft S-radicals, and (iii) hydrophobic preference for neutral (thyil radical) over charged (thiolate) species in the immediate Rf catalytic environment. Steric crowding could destabilize [RS ^~ — Co(H)Pc], which may exhibit an approximately 2.2 A Co-S bond (see, e.g., Cardenas-Jiron, G. I. et al., J. Mol. Struct., 580, 193 (2002)), the sp ³ hybridized S forcing the thiolate backbone too close to the R _f groups. This destabilization generally vanishes upon electron transfer and departure of the resulting thyil radical. Thus, the results suggest that 3-Co appears to exhibit strong RS-Co binding, a potential "deficiency", but which could be used to broaden its reactivity spectrum to include less basic thiols.

[00142] This use also provides an alternative exemplary thiol coupling. In particular, perfluoro benzenethiol (hereinafter "PBT") is a poor nucleophiie, at least one million times more acidic than 2-ME, their pKa values being about 2.68 and about 9.2, respectively (see, e.g., Martell, A. E. et al., Critical Stability Constants, vol. 3, Plenum Press, New York (1977)). Thus, the critical steps of thiolate coordination and electron transfers may not occur for PBT. Indeed, to the best of our knowledge, the aerobic coupling of PBT has not been reported. No oxidation was observed with 1-Co, unlike the case of 2-ME. In contrast, 3-Co produces PBT disulfide (identified by ^l9 F NMR), approximately 6.4 times faster than 2-Co with an yield about 1.6 times as high, about 53% and about 32%, respectively (see FIG. 39). The low yields are due to a parallel, unrelated reaction of the PBT anion, C ₆ F ₅ S ^~ , which dimerizes via nucleophilic attack to yield the thioether-thiol C ₆ F ₅ S- J-C ₆ p ₄ S ^~ (see, e.g., Namuswe, F. et al., J. Am. Chem. Soc , 130, 141 89 (2008)). Further, glass corrosion was observed, potentially due to HF. Consequently, the PBT anion concentration decreases ( ¹⁹ F NMR), consistently with the lower total (¾ uptake.

[00143] The extreme electronic deficiency of 3-Co is actually beneficial in securing efficient binding of an acidic thiol and subsequent electron transfer, events that typically do not occur with the parent 1 -Co, or occur less efficiently with the sterically unhindered and electronically richer (relative to 3-Co) 2-Co.

[00144] Despite F^Pc scaffold electronic deficiency, activation of C½ generally occurs within the Rf pocket of 3-Co by two, one-electron transfer steps to form (¾ ^" and (¾ ² . The Fg ₄ Pc ligand is thus able to suppress electron loss from Co(II), but not from Co(I). The 1 : 1 F:R _f ratio appears suitable for both catalyst stability and activity in certain disclosed embodiments of the present invention. Its lowering might prevent electron loss even from the Co(I) level, thus stopping the catalysis, while its increase could lead to catalyst instability. Notably, the stepwise reduction of (¾ to (¾ ³ without disproportionation is known for the N ₄ S(thiolate) chromophore of superoxide reductases (SOR), but with = Fe. Strong trans thioiate binding is believed to weaken the -0 bond, thus favoring the release of ¾(¾ (see, e.g., Namuswe, F. et al., J. Am. Chem. Soc, 130, 14189 (2008)), an effect relevant to the present disclosure since ¾<¾ released from the Co center contributes to thiol coupling.

[00145] In summary, disclosed is a first member of a family of three-dimensional, metal- organic aerobic catalysts whose organic ligand framework is designed to stabilize it against all possible degradation pathways. Coordination and reduction of <¾ within a fluorinated active site pocket leads to both O- and S-centered radicals, the latter coupling to disulfides.

[00146] Further, the stabilization of ligand composition, while offering labile sites for catalysis, is also a challenge that responds to identified future technology needs (see, e.g., Lippard, S. J., Nature, 416, 587 (2002)). In particular, the fluoro-perfluoroalkyl substituents offer an answer within phthalocyanines and, maybe, other frameworks.

[00147] In one exemplary embodiment of the present invention we have a process in which the catalyst is a chemically robust phthalocyanine in which all C-H bonds of said molecule have been replaced by a combination of F and perfluoro-isopropyl groups and which displays a redox metal center with high Lewis acidity.

[00148] The properties of the phthalocyanines described above show how the industrial process of oxidative coupling of corrosive thiols to disulfides, i.e., petroleum sweetening, can be advantageously improved by the novel and highly-stable, yet active, catalyst class. Some potentially advantageous properties of the disclosed exemplary catalysts include, but are not limited to, e.g., lower need for catalyst replacement, spent catalyst separations, disposal cost, and the like.

[00149] Although the present disclosure has been described with reference to exemplary embodiments and implementations, it is to be understood that the present disclosure is neither limited by nor restricted to such exemplary embodiments and/or implementations. Rather, the present disclosure is susceptible to various modifications, enhancements and variations without departing from the spirit or scope of the present disclosure. Indeed, the present disclosure expressly encompasses such modifications, enhancements and variations as will be readily apparent to persons skilled in the art from the disclosure herein contained.