Photosynthetica 2018, 56(1):67-74 | DOI: 10.1007/s11099-018-0783-y

Synthesis and characterization of a cobalt(II) tetrakis(3-fluorophenyl) porphyrin with a built-in 4-vinylphenyl surface attachment moiety

D. Khusnutdinova1, M. Flores1, A. M. Beiler1, G. F. Moore1,*
1 School of Molecular Sciences and the Biodesign Institute Center for Applied Structural Discovery (CASD), Arizona State University, Tempe, USA

Metalloporphyrins serve important roles in biology and as components in emerging technological assemblies for energy conversion. In this report, we describe the synthesis and characterization of a novel cobalt(II) 5,10,15,20-tetrakis (3-fluorophenyl)porphyrin bearing a 4-vinylphenyl surface attachment group at a beta position on the macrocycle. Electrochemical measurements show the 3-fluorophenyl groups at the meso positions of the porphyrin perturb the reduction potentials of the complex to more positive values as compared to non-fluorinated analogs, thus allowing access to reduced cobalt porphyrin species at significantly less negative applied bias potentials. The complex, cobalt(II) 5,10,15,20-tetrakis(3-fluorophenyl)-2-(4-vinylphenyl)porphyrin, is abbreviated in this article as Gov-1 in honor of Govindjee for his pioneering investigations in the role of fluorine as a promoter of novel protein-substrate interactions and the inspirational role he continues to have in encouraging young investigators in the areas of natural and artificial photosynthesis.

Additional key words: artificial photosynthesis; fluorine; porphyrins; surface chemistry

Received: June 30, 2017; Accepted: September 5, 2017; Published: March 1, 2018  Show citation

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Khusnutdinova, D., Flores, M., Beiler, A.M., & Moore, G.F. (2018). Synthesis and characterization of a cobalt(II) tetrakis(3-fluorophenyl) porphyrin with a built-in 4-vinylphenyl surface attachment moiety. Photosynthetica, 56(SPECIAL ISSUE), 67-74. doi: 10.1007/s11099-018-0783-y
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    References

    1. Adler A.D., Longo F.R., Finarelli J.D. et al: A simplified synthesis for meso-tetraphenylporphyrin.-J. Org. Chem. 32: 476, 1966. Go to original source...
    2. Alben J.O., Choi S.S., Adler A.D. et al.: Infrared spectroscopy of porphyrins.-Ann. NY Acad. Sci. 206: 278-295, 1973. Go to original source...
    3. Bard A.J., Fox M.A.: Artificial photosynthesis: solar splitting of water to hydrogen and oxygen.-Acc. Chem. Res. 28: 141-145, 1995. Go to original source...
    4. Behar D., Dhanasekaran T., Neta P et al.: Cobalt porphyrin catalyzed reduction of CO2 radiation chemical, photochemical, and electrochemical studies.-J. Phys. Chem. A 102: 2870-2877, 1998. Go to original source...
    5. Beiler A.M., Khusnutdinova D., Jacob S.I. et al.: Solar hydrogen production using molecular catalysts immobilized on gallium phosphide (111)A and (111)B polymer-modified photocathodes.-ACS Appl. Mater. Interfaces 8: 10038-10047, 2016a. Go to original source...
    6. Beiler A.M., Khusnutdinova D., Jacob S.I. et al.: Chemistry at the interface: polymer-functionalized GaP semiconductors for solar hydrogen production.-Ind. Eng. Chem. Res. 55: 5306-5314, 2016b. Go to original source...
    7. Beiler A.M., Khusnutdinova D., Wadsworth B.L. et al.: Cobalt porphyrin-polypyridyl surface coatings for photoelectrosynthetic hydrogen production.-Inorg. Chem. 56: 12178-12185, 2017. Go to original source...
    8. Berben L.A., Peters J.C.: Hydrogen evolution by cobalt tetraimine catalysts adsorbed on electrode surfaces.-Chem. Commun. 46: 398-400, 2010. Go to original source...
    9. Boucher L.J., Katz J.J.: The infared spectra of metalloporphyrins (4000-160 [cm-1]).-J. Am. Chem. Soc. 89: 1340-1345, 1967. Go to original source...
    10. Blankenship R.E., Tiede D.M., Barber J. et al.: Comparing photosynthetic and photovoltaic efficiencies and recognizing the potential for improvement.-Science 332: 805-809, 2011. Go to original source...
    11. Cedeno D., Krawicz A., Doak P. et al.: Using molecular design to control the performance of hydrogen producing polymerbrush-modified photocathodes.-J. Phys. Chem. Lett. 5: 3222-3226, 2014. Go to original source...
    12. Cedeno D., Krawicz A., Moore G.F.: Hybrid photocathodes for solar fuel production: coupling molecular fuel-production catalysts with solid-state light harvesting and conversion technologies.-Interface Focus 5: 20140085, 2015. Go to original source...
    13. Chambers R.D.: Fluorine in Organic Chemistry. Pp. 384. Blackwell Publishing Ltd. Oxford 2004. Go to original source...
    14. Chapman R.D., Fleischer E.B.: Direct measurement of electron self-exchange rates of cobalt porphyrins. 1. Outer-sphere exchange.-J. Am. Chem. Soc. 104: 1575-1582, 1982. Go to original source...
    15. Cicero R.L., Linford M.R., Chidsey C.E.D.: Photoreactivity of unsaturated compounds with hydrogen-terminated silicon (111).-Langmuir 16: 5688-5695, 2000. Go to original source...
    16. Dalvit C., Vulpetti A.: Fluorine-protein interactions and 19F NMR isotopic chemical shifts: an empirical correlation with implication for drug design.-Chem. Med. Chem. 6: 104-114, 2011. Go to original source...
    17. Dhanasekaran T., Grodkowski J., Neta P. et al.: p-terphenylsensitized photoreduction of CO2 with cobalt and iron porphyrins. Interaction between CO and reduced metalloporphyrins.-J. Phys. Chem. A 103: 7742-7748, 1999. Go to original source...
    18. Faunce T.A., Lubitz W., Rutherford A.W. et al.: Energy and environment policy case for a global project on artificial photosynthesis.-Energy Environ. Sci. 6: 695-698, 2013a. Go to original source...
    19. Faunce T.A., Styring S., Wasiełewski M.R. et al.: Artificial photosynthesis as a frontier technology for energy sustainability.-Energy Environ. Sci. 6: 1074-1076, 2013b. Go to original source...
    20. Flores M., Isaacson R., Abresch E. et al.: Protein-cofactor interactions in bacterial reaction centers from Rhodobacter sphaeroides R-26: II. Geometry of the hydrogen bonds to the primary quinone QA.-by 1H and 2H ENDOR spectroscopy.-Biophys. J. 92: 671-682, 2007. Go to original source...
    21. Gerig J.T.: Fluorine magnetic resonance in biochemistry.-In: Berliner L.J., Reuben J. (ed.): Biological Magnetic Resonance (A Series of Contemporary Topics and Reviews), Vol. 1. Pp. 139-203, Springer, New York 1978. Go to original source...
    22. Gobi K.V., Tokuda K., Ohsaka T.: Electrochemical and spectroscopic studies on nickel(II/III) complexes with novel 14-membered hexaaza macrocycle functionalized with propenyl groups.-Electrochim. Acta 43: 1013-1022, 1998. Go to original source...
    23. Govindjee: Celebrating Andrew Alm Benson's 93rd birthday.-Photosynth. Res. 105: 201-208, 2010. Go to original source...
    24. Govindjee: Young research investigators honored at the 2008 and 2009 Gordon research conferences on photosynthesis: ambiance and a personal perspective.-Photosynth. Res. 102: 1-6, 2009. Go to original source...
    25. Govindjee, Ananyev G.M., Savikhin S.: Young research investigators honored at the 2011 Gordon research conference on photosynthesis: ambiance and a perspective.-Photosynth. Res. 110: 143-149, 2011. Go to original source...
    26. Govindjee, Rutherford A.W., Britt R.D.: Four young research investigators were honored at the 2006 Gordon research conference on photosynthesis.-Photosynth. Res. 92: 137-138, 2007. Go to original source...
    27. Govindjee, ©esták Z., Peters W.R.: The early history of "Photosynthetica", "Photosynthesis Research", and their publishers.-Photosynthetica 40: 1-11, 2002. Go to original source...
    28. Govindjee, Telfer A.: Six young research investigators were honored at an international conference in Russia.-Photosynth. Res. 92: 139-141, 2007. Go to original source...
    29. Hou H.J.M., Najafpour M.M., Moore G.F. et al.: Photosynthesis: Structures, Mechanisms, and Applications. Pp. 321-358. Springer, New York 2017. Go to original source...
    30. Kadish K.M., Caemelbecke E.V.: Electrochemistry of porphyrins and related macrocycles.-J. Solid State Electrochem. 7: 254-258, 2003. Go to original source...
    31. Khusnutdinova D., Beiler A.M., Wadsworth B.L. et al.: Metalloporphyrin-modified semiconductor for solar fuel production.-Chem. Sci. 8: 253-259, 2017. Go to original source...
    32. Kim C.-Y., Chang J.S., Doyon J.B. et al.: Contribution of fluorine to protein-ligand affinity in the binding of fluoroaromatic inhibitors to carbonic anhydrase II.-J. Am. Chem. Soc. 122: 12125-12134, 2000. Go to original source...
    33. Kincaid J., Nakamoto K.: Vibrational spectra of transition metal complexes of tetraphenylporphine.-J. Inorg. Nucl. Chem. 37: 85-89, 1975. Go to original source...
    34. Li B., Franking R., Landis E.C. et al.: Photochemical grafting and patterning of biomolecular layers onto TiO2 thin films.-ACS Appl. Mater. Interfaces. 1: 1013-1022, 2009. Go to original source...
    35. Luca O.R., Crabtree R.H.: Redox-active ligands in catalysis.-Chem. Soc. Rev. 42: 1440-1459, 2013. Go to original source...
    36. Lyaskovskyy V., de Bruin B.: Redox non-innocent ligands: versatile new tools to control catalytic reactions.-ACS Catal. 2: 270-279, 2012. Go to original source...
    37. Maher A.G., Passard G., Dogutan D.K. et al.: Hydrogen evolution catalysis by a sparsely substituted cobalt chlorin.-ACS Catal. 7: 3597-3606, 2017. Go to original source...
    38. Moore G.F.: Concluding remarks and future perspectives: looking back and moving forward. Pp. 407-414. Springer, New York 2017. Go to original source...
    39. Moore G.F., Ananyev G.M., Govindjee: Young research investigators honored at the 2012 Gordon Research Conference on Photosynthesis-Photosynth. Res. 114: 137-142, 2012a. Go to original source...
    40. Moore G.F., Hambourger M., Gervaldo M. et al: A bioinspired construct that mimics the proton coupled electron transfer between P680*+ and the Tyrz-His 190 pair of photosystem II.-J. Am. Chem. Soc. 130: 10466-10467, 2008. Go to original source...
    41. Moore G.F., Konezny S.J., Song H. et al.: Bioinspired highpotential porphyrin photoanodes.-J. Phys. Chem. C 116: 4892-4902, 2012b. Go to original source...
    42. Moore G.F., Sharp I.D.: A noble-metal-free hydrogen evolution catalyst grafted to visible light-absorbing semiconductors.-J. Phys. Chem. Lett. 4: 568-572, 2013. Go to original source...
    43. Najafpour M.M., Shen J-R., Barber J. et al.: Running on sun.-Chem. World November: 43, 2012.
    44. Nguyen K., Day P.N., Pachter R.: Effects of halogenation on the ionized and excited states of free-base and zinc porphyrins.-J. Chem. Phys. 110: 9135-9144, 1999. Go to original source...
    45. O'Hagan D., Rzepa H. S.: Some influences of fluorine in bioorganic chemistry.-Chem. Commun. 7: 645-652, 1997. Go to original source...
    46. Rappaport F., Malnoë A., Govindjee: Gordon research conference on photosynthesis: from evolution of fundamental mechanisms to radical re-engineering.-Photosynth. Res. 123: 213-223, 2015. Go to original source...
    47. Richards D., Zemlyanov D., Ivanisevic A.: Assessmnet of the passivation capabilities of two different covalent chemical modifications on GaP(100).-Langmuir 26: 8141-8146, 2010. Go to original source...
    48. Rose M.J., Gray H.B., Winkler J.R.: Hydrogen generation catalyzed by fluorinated diglyoxime-iron complexes at low overpotentials.-J. Am. Chem. Soc. 134: 8310-8313, 2012. Go to original source...
    49. Rosenthal J., Luckett T.D., Hodgkiss J.M. et al.: Photocatalytic oxidation of hydrocarbons by a bis-iron(III)-μ-oxo pacman porphyrin using O2 and visible light.-J. Am. Chem. Soc. 128: 6546-6547, 2006. Go to original source...
    50. Seifert M., Koch A.H.R., Deubel F. et al.: Functional polymer brushes on hydrogenated graphene.-Chem. Mater. 25: 466-470, 2013. Go to original source...
    51. Słota R., Broda M.A., Dyrda G. et al.: Structural and molecular characterization of meso-substituted zinc porphyrins: a DFT supported study.-Molecules 16: 9957-9971, 2011. Go to original source...
    52. Steenackers M., Gigler A.M., Zhang N. et al.: Polymer brushes on graphene.-J. Am. Chem. Soc. 133: 10490-10498, 2011. Go to original source...
    53. Stoll, S., Schweiger, A.: EasySpin, a comprehensive software package for spectral simulation and analysis in EPR.-J. Magn. Reson. 178: 42-55, 2006. Go to original source...
    54. Sun H., Smirnov V., DiMagno S.G.: Slow electron transfer rates for fluorinated cobalt porphyrins: electronic and conformational factors modulating metalloporphyrin ET.-Inorg. Chem. 42: 6032-6040, 2003. Go to original source...
    55. Sykes B.D., Hull W.E., Snyder G.H.: Experimental evidence for role of cross-relaxation in proton nuclear magnetic resonance spin lattice relaxation time measurements in proteins.-Biophys. J. 21: 137-146, 1978. Go to original source...
    56. Tierno M.E., Mead D., Asato A.E. et al.: 14-fluorobacteriorhodopsin and other fluorinated and 14-substituted analogues. An extra, unusually red-shifted pigment formed during dark adaptation.-Biochemistry 29: 5948-5953, 1990. Go to original source...
    57. Toi H., Homma M., Suzuki A. et al.: Paramagnetic 19F N.M.R. spectra of iron(III) porphyrins substituted with CF3 groups and reconstituted myoglobin.-J. Chem. Soc. Chem. Comm. 24: 1791-1792, 1985. Go to original source...
    58. Tomkowicz Z., Rams M., Bałanda M. et al.: Slow magnetic relaxations in manganese(III) tetra(meta-fluorophenyl)-porphyrin-tetracyanoethenide. Composition with the relative single chain magnet ortho compound.-Inorg. Chem. 51: 9983-9994, 2012. Go to original source...
    59. Wadsworth B.L., Beiler A.M., Khusnutdinova D. et al.: Electrocatalytic and optical properties of cobaloxime catalysts immobilized at a surface-grafted polymer interface.-ACS Catal. 6: 8048-8057, 2016. Go to original source...
    60. Yolder N.C., Kumar K.: Fluorinated amino acids in protein design and engineering.-Chem. Soc. Rev. 31: 335-341, 2002. Go to original source...

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