131
132
The electrochemistry of the Tin porphyrins were analyzed cyclic voltammetry. The Pourbaix diagram were constructed which was characterized by stepwise increase of oxidation potential supporting the stepwise protonation of axial and peripheral groups observed by the spectrophotometric titration.
The catalytic turn over frequencies of tin porphyrins were calculated by the modified Randless- Sevcik method. SnTPyP exhibit excellent TOF in acidic pH whereas SnTMPyP shows good TOF in basic, neutral and buffered conditions. The DFT calculation shows that the enhancement of TOF of the axially deprotonated forms is due to the spin localization on the axial oxygen atom. Bulk electrolysis of SnTMPyP under basic, carbonate buffer and phosphate buffer conditions has been carried out. Hydrogen, oxygen, and hydrogen peroxide were detected with good faradaic yield. The chemical structural change of SnTMPyP was analyzed by performing the CPE in deuterated water under basic pH. The two electron electrochemical water oxidation mechanism has been proposed. The equilibrium constant for the reaction between SnTMPyP and hydrogen peroxide were measured by UV-Vis spectroscopy towards the identification intermediate tin peroxo complex formed during water oxidation catalyzed by Tin porphyrins. CPE experiments would be inspiring for other Tin porphyrins especially for SnTPyP which exhibit good turnover frequency in the acidic pH.
Tin porphyrins and TiO2/SnO2 hybrids were prepared by axial and ionic coordination. The electron injection efficiency was investigated by Iodide experiments. It indicates that the tin porphyrins can inject electrons more efficiently to SnO2 than TiO2. Taking inspiration from these experiments direct photoelectrochemical water oxidation was carried out by irradiating the SnP-SnO2 semiconductor hybrid. Hydrogen and hydrogen peroxide were detected quantitatively in buffered condition
133
Summary
A new facile synthetic procedure for water soluble and insoluble cationic tin porphyrins was discovered and the reaction mechanism was well investigated.
The multiptotolytic equilibria of axial and peripheral groups of Tin porphyrins were analyzed by UV-Vis, Emission and 1H NMR spectroscopy.
The electrochemistry of Tin porphyrins was well understood by constructing the Pourbaix diagrams.
The catalytic turn over frequency was estimated by modified Randless –Sevcik method. The electrochemical water oxidation tin porphyrins were carried out and Hydrogen, oxygen and hydrogen peroxide were detected with good faradaic yield.
The tin porphyrin-TiO2/SnO2 hybrids were prepared and photoelectrolysis were carried out towards photoelectrochemical water oxidation.Future prospects
Exploration of other tin porphyrins toward electrochemical and photoelectrochemical water oxidation.
The photoelectrochemical studies of SnTMPyP in semiconductor systems.
The coupling of the tin porphyrin water oxidation systems with carbon dioxide reduction setup for the systemization of the artificial photosynthesis.
Investigation of the water oxidation mechanism of Tin porphyrins by laser flash photolysis.134
References
(1) Powering The World With Sunlight. A White Paper Describing the Discussions and Outcomes of the 1st Annual Chemical Sciences and Society Symposium Available from https://www3.csj.jp/news/cs3-whitepaper.pdf 2009
(2) Sekar, N.; Ramasamy, R. P. Journal of Photochemistry and Photobiology C:
Photochemistry Reviews 2015, 22, 19.
(3) Mann, M. E.; Bradley, R. S.; Hughes, M. K. Nature 1998, 392, 779.
(4) Kamat, P. V. the Journal of Physical Chemistry C 2007, 111, 2834.
(5) Balzani, V.; Credi, A.; Venturi, M. ChemSusChem 2008, 1, 26.
(6) Crabtree, G. Energy Research Group Presentations 2007, 2.
(7) Gust, D.; Moore, T. A.; Moore, A. L. Accounts of chemical research 2009, 42, 1890.
(8) Hoffert, M. I.; Caldeira, K.; Benford, G.; Criswell, D. R.; Green, C.; Herzog, H.; Jain, A.
K.; Kheshgi, H. S.; Lackner, K. S.; Lewis, J. S. science 2002, 298, 981.
(9) Barber, J. Chemical Society Reviews 2009, 38, 185.
(10) Hill, R. Proceedings of the Royal Society of London. Series B, Biological Sciences 1939, 127, 192.
(11) Hill, R.; Bendall, F. A. Y., Function of Two Cytochrome Components in Chloroplasts:
A Working Hypotheis, Nature 1960, 186,136.
(12) Umena, Y.; Kawakami, K.; Shen, J.-R.; Kamiya, N. Nature 2011, 473, 55.
(13) Kok, B.; Forbush, B.; McGloin, M. Photochemistry and Photobiology 1970, 11, 457.
(14) Kuttassery, F.; Mathew, S.; Yamamoto, D.; Onuki, S.; Nabetani, Y.; Tachibana, H.; Inoue, H. Electrochemistry 2014, 82, 475.
135
(15) Inoue, H.; Shimada, T.; Kou, Y.; Nabetani, Y.; Masui, D.; Takagi, S.; Tachibana, H.
ChemSusChem 2011, 4, 173.
(16) Kou, Y.; Nakatani, S.; Sunagawa, G.; Tachikawa, Y.; Masui, D.; Shimada, T.; Takagi, S.;
Tryk, D. A.; Nabetani, Y.; Tachibana, H. Journal of Catalysis 2014, 310, 57.
(17) Fujishima, A.; Honda, K. Nature 1972, 238, 37.
(18) Gersten, S. W.; Samuels, G. J.; Meyer, T. J. Journal of the American Chemical Society 1982, 104, 4029.
(19) Hawecker, J.; Lehn, J.-M.; Ziessel, R. Journal of the Chemical Society, Chemical Communications 1983, 536.
(20) Hawecker, J.; Lehn, J. M.; Ziessel, R. Helvetica chimica acta 1986, 69, 1990.
(21) Yang, L.; Zhou, H.; Fan, T.; Zhang, D. Physical Chemistry Chemical Physics 2014, 16, 6810.
(22) Tachibana, Y.; Vayssieres, L.; Durrant, J. R. Nature Photonics 2012, 6, 511.
(23) Kudo, A.; Miseki, Y. Chemical Society Reviews 2009, 38, 253.
(24) Abe, R. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2010, 11, 179.
(25) Domen, K.; Naito, S.; Soma, M.; Onishi, T.; Tamaru, K. Journal of the Chemical Society, Chemical Communications 1980, 543.
(26) Kudo, A.; Domen, K.; Maruya, K.-i.; Onishi, T. Chemical physics letters 1987, 133, 517.
(27) Sayama, K.; Arakawa, H. Journal of the Chemical Society, Faraday Transactions 1997, 93, 1647.
(28) Kato, H.; Kudo, A. The Journal of Physical Chemistry B 2001, 105, 4285.
(29) Kato, H.; Kudo, A. Chemical physics letters 1998, 295, 487.
136
(30) Walsh, A.; Yan, Y.; Huda, M. N.; Al-Jassim, M. M.; Wei, S.-H. Chemistry of Materials 2009, 21, 547.
(31) Kudo, A.; Omori, K.; Kato, H. Journal of the American Chemical Society 1999, 121, 11459.
(32) Shimodaira, Y.; Kato, H.; Kobayashi, H.; Kudo, A. The Journal of Physical Chemistry B 2006, 110, 17790.
(33) Kadowaki, H.; Saito, N.; Nishiyama, H.; Kobayashi, H.; Shimodaira, Y.; Inoue, Y. the Journal of Physical Chemistry C 2007, 111, 439.
(34) Wang, D.; Tang, J.; Zou, Z.; Ye, J. Chemistry of Materials 2005, 17, 5177.
(35) Fillol, J. L.; Codolà, Z.; Garcia-Bosch, I.; Gómez, L.; Pla, J. J.; Costas, M. Nature chemistry 2011, 3, 807.
(36) Barnett, S. M.; Goldberg, K. I.; Mayer, J. M. Nature chemistry 2012, 4, 498.
(37) Arafa, W.; Kärkäs, M.; Lee, B. Phys. Chem. Chem. Phys 2014, 16, 11950.
(38) Yagi, M.; Syouji, A.; Yamada, S.; Komi, M.; Yamazaki, H.; Tajima, S. Photochemical &
Photobiological Sciences 2009, 8, 139.
(39) Surendranath, Y.; Dinca, M.; Nocera, D. G. Journal of the American Chemical Society 2009, 131, 2615.
(40) Zong, R.; Thummel, R. P. Journal of the American Chemical Society 2005, 127, 12802.
(41) Wada, T.; Tsuge, K.; Tanaka, K. Angewandte Chemie 2000, 112, 1539.
(42) Yagi, M.; Tajima, S.; Komi, M.; Yamazaki, H. Dalton Transactions 2011, 40, 3802.
(43) Duan, L.; Bozoglian, F.; Mandal, S.; Stewart, B.; Privalov, T.; Llobet, A.; Sun, L. Nature chemistry 2012, 4, 418.
(44) Yamada, H.; Siems, W. F.; Koike, T.; Hurst, J. K. Journal of the American Chemical Society 2004, 126, 9786.
137
(45) Wada, T.; Tsuge, K.; Tanaka, K. Inorganic chemistry 2001, 40, 329.
(46) Muckerman, J. T.; Polyansky, D. E.; Wada, T.; Tanaka, K.; Fujita, E. Inorganic chemistry 2008, 47, 1787.
(47) Kurimoto, K.; Yamazaki, T.; Suzuri, Y.; Nabetani, Y.; Onuki, S.; Takagi, S.; Shimada, T.;
Tachibana, H.; Inoue, H. Photochemical & Photobiological Sciences 2014, 13, 154.
(48) Shiragami, T.; Nakamura, H.; Matsumoto, J.; Yasuda, M.; Suzuri, Y.; Tachibana, H.; Inoue, H. Journal of Photochemistry and Photobiology A: Chemistry 2015, 313, 131.
(49) Mathew, S.; Kuttassery, F.; Gomi, Y.; Yamamoto, D.; Kiyooka, R.; Onuki, S.; Nabetani, Y.; Tachibana, H.; Inoue, H. Journal of Photochemistry and Photobiology A: Chemistry 2015, 313, 137.
(50) Remello, S. N.; Kuttassery, F.; Hirano, T.; Nabetani, Y.; Yamamoto, D.; Onuki, S.;
Tachibana, H.; Inoue, H. Dalton Transactions 2015, 44, 20011.
(51) Remello, S. N.; Hirano, T.; Kuttassery, F.; Nabetani, Y.; Yamamoto, D.; Onuki, S.;
Tachibana, H.; Inoue, H. Journal of Photochemistry and Photobiology A: Chemistry 2015, 313, 176.
(52) Duan, L.; Wang, L.; Inge, A. K.; Fischer, A.; Zou, X.; Sun, L. Inorganic chemistry 2013, 52, 7844.
(53) Coggins, M. K.; Zhang, M.-T.; Vannucci, A. K.; Dares, C. J.; Meyer, T. J. Journal of the American Chemical Society 2014, 136, 5531.
(54) Wang, D.; Groves, J. T. Proceedings of the National Academy of Sciences 2013, 110, 15579.
(55) Artero, V.; Chavarot‐Kerlidou, M.; Fontecave, M. Angewandte Chemie International Edition 2011, 50, 7238.
138
(56) Zhang, T.; Wang, C.; Liu, S.; Wang, J.-L.; Lin, W. Journal of the American Chemical Society 2013, 136, 273.
(57) Garrido-Barros, P.; Funes-Ardoiz, I.; Drouet, S.; Benet-Buchholz, J.; Maseras, F.; Llobet, A. Journal of the American Chemical Society 2015, 137, 6758.
(58) Das, A. K.; Engelhard, M. H.; Bullock, R. M.; Roberts, J. A. Inorganic chemistry 2014, 53, 6875.
(59) Inoue, H.; Funyu, S.; Shimada, Y.; Takagi, S. Pure and applied chemistry 2005, 77, 1019.
(60) Funyu, S.; Isobe, T.; Takagi, S.; Tryk, D. A.; Inoue, H. Journal of the American Chemical Society 2003, 125, 5734.
(61) Shimada, T.; Kumagai, A.; Funyu, S.; Takagi, S.; Masui, D.; Nabetani, Y.; Tachibana, H.;
Tryk, D. A.; Inoue, H. Faraday discussions 2012, 155, 145.
(62) Funyu, S.; Kinai, M.; Masui, D.; Takagi, S.; Shimada, T.; Tachibana, H.; Inoue, H.
Photochemical & Photobiological Sciences 2010, 9, 931.
(63) Takagi, S.; Eguchi, M.; Tryk, D. A.; Inoue, H. Langmuir 2006, 22, 1406.
(64) Mathew, S.; Kuttassery, F.; Yamamoto, D.; Onuki, S.; Nabetani, Y.; Tachibana, H.; Inoue, H. Bulletin of the Chemical Society of Japan 2016, 89, 334.
(65) Takagi, S.; Suzuki, M.; Shiragami, T.; Inoue, H. Journal of the American Chemical Society 1997, 119, 8712.
(66) Inoue, H.; Sumitani, M.; Sekita, A.; Hida, M. Journal of the Chemical Society, Chemical Communications 1987, 1681.
(67) Inoue, H.; Okamoto, T.; Komiyama, M.; Hida, M. Journal of Photochemistry and Photobiology A: Chemistry 1992, 65, 221.
139
(68) Inoue, H.; Okamoto, T.; Kameo, Y.; Sumitani, M.; Fujiwara, A.; Ishibashi, D.; Hida, M.
Journal of the Chemical Society, Perkin Transactions 1 1994, 105.
(69) Shiragami, T.; Kubomura, K.; Ishibashi, D.; Inoue, H. Journal of the American Chemical Society 1996, 118, 6311.
(70) Takagi, S.; Morimoto, H.; Shiragami, T.; Inoue, H. Research on Chemical Intermediates 2000, 26, 171.
(71) Kim, W.; Park, J.; Jo, H. J.; Kim, H.-J.; Choi, W. the Journal of Physical Chemistry C 2008, 112, 491.
(72) Kim, W.; Tachikawa, T.; Majima, T.; Li, C.; Kim, H.-J.; Choi, W. Energy & Environmental Science 2010, 3, 1789.
(73) Wang, S.; Tabata, I.; Hisada, K.; Hori, T. Dyes and pigments 2002, 55, 27.
(74) Wang, S.; Tabata, I.; Hisada, K.; Hori, T. Journal of Porphyrins and Phthalocyanines 2003, 7, 199.
(75) Manke, A.-M.; Geisel, K.; Fetzer, A.; Kurz, P. Physical Chemistry Chemical Physics 2014, 16, 12029.
(76) Moghadam, M.; Tangestaninejad, S.; Mirkhani, V.; Mohammadpoor-Baltork, I.; Gharaati, S. Inorganica chimica acta 2010, 363, 1523.
(77) Shaegh, S. A. M.; Nguyen, N.-T.; Ehteshami, S. M. M.; Chan, S. H. Energy &
Environmental Science 2012, 5, 8225.
(78) Thomas, A.; Kuttassery, F.; Remello, S. N.; Mathew, S.; Yamamoto, D.; Onuki, S.;
Nabetani, Y.; Tachibana, H.; Inoue, H. Bulletin of the Chemical Society of Japan 2016, 89, 902.
(79) Arnold, D. P.; Blok, J. Coordination chemistry reviews 2004, 248, 299.
140
(80) Shetti, V. S.; Pareek, Y.; Ravikanth, M. In Coordination chemistry reviews 2012; Vol. 256, p 2816.
(81) Jo, H.-J.; Jung, S.-H.; Kim, H.-J. Bulletin of the Korean Chemical Society 2004, 25, 1869.
(82) Ghiggino, K. P.; Giri, N. K.; Hanrieder, J.; Martell, J. D.; Müller, J.; Paige, M. F.;
Robotham, B.; Szmytkowski, J.; Steer, R. P. The Journal of Physical Chemistry A 2013, 117, 7833.
(83) Rothemund, P.; Menotti, A. R. Journal of the American Chemical Society 1948, 70, 1808.
(84) Shetti, V. S.; Ravikanth, M. Journal of Porphyrins and Phthalocyanines 2010, 14, 361.
(85) Gouterman, M.; Schwarz, F. P.; Smith, P. D.; Dolphin, D. The Journal of Chemical Physics 1973, 59, 676.
(86) Adler, A. D.; Longo, F. R.; Kampas, F.; Kim, J. Journal of Inorganic and Nuclear Chemistry 1970, 32, 2443.
(87) Crossley, M. J.; Thordarson, P.; Wu, R. A.-S. Journal of the Chemical Society, Perkin Transactions 1 2001, 2294.
(88) Durmuş, M.; Nyokong, T. Photochemical & Photobiological Sciences 2007, 6, 659.
(89) Oppelt, K. T.; Wöß, E.; Stiftinger, M.; Schöfberger, W.; Buchberger, W.; Knör, G. n.
Inorganic chemistry 2013, 52, 11910.
(90) Harriman, A.; Porter, G.; Walters, P. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1983, 79, 1335.
(91) Kano, K.; Nakajima, T.; Takei, M.; Hashimoto, S. Bulletin of the Chemical Society of Japan 1987, 60, 1281.
(92) Kano, K.; Minamizono, H.; Kitae, T.; Negi, S. The Journal of Physical Chemistry A 1997, 101, 6118.
141
(93) Kano, K.; Fukuda, K.; Wakami, H.; Nishiyabu, R.; Pasternack, R. F. Journal of the American Chemical Society 2000, 122, 7494.
(94) Whitten, D. G.; Yau, J. C. Tetrahedron Letters 1969, 10, 3077.
(95) Wang, X.; Gray, S. D.; Chen, J.; Woo, L. K. Inorganic chemistry 1998, 37, 5.
(96) Landrum, J. T.; Amini, M.; Zuckerman, J. Inorganica chimica acta 1984, 90, L73.
(97) Barbe, J.; Ratti, C.; Richard, P.; Lecomte, C.; Gerardin, R.; Guilard, R. Inorganic chemistry 1990, 29, 4126.
(98) Kadish, K.; Dubois, D.; Barbe, J.; Guilard, R. Inorganic chemistry 1991, 30, 4498.
(99) Feiner, A.-S.; McEvoy, A. J. Chem. Educ 1994, 71, 493.
(100) Meyer, T. J.; Huynh, M. H. V.; Thorp, H. H. Angewandte Chemie International Edition 2007, 46, 5284.
(101) Warner Instrument Corporation, White Paper, Salt Bridge Form, Rev.9.1.99.,1999, https://www.warneronline.com/pdf/whitepapers/agar_bridges.pdf;
(102) URl;https://chemwisc.edu/deptfiles/genchem/lab/labdocs/modules/echem/echemsalt.html;
. Chem Pages Laboratory Sources
(103) Takamura, K.; Matsubara, C. Bulletin of the Chemical Society of Japan 2003, 76, 1873.
(104) Gaussian 09, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M.
A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H.
Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L.
Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand,K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J.