A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies
- 주제(기타) Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary
- 설명문(일반) [Suzuki, Wataru; Kotani, Hiroaki; Ishizuka, Tomoya; Kojima, Takahiko] Univ Tsukuba, Fac Pure & Appl Sci, Dept Chem, 1-1-1 Tennoudai, Tsukuba, Ibaraki 3058571, Japan; [Kawano, Masaki] Tokyo Inst Technol, Sch Sci, Dept Chem, Meguro Ku, 2-12-1 Ookayama, Tokyo 1528550, Japan; [Sakai, Hayato; Hasobe, Taku] Keio Univ, Fac Sci & Technol, Dept Chem, Yokohama, Kanagawa 2238522, Japan; [Ohkubo, Kei] Osaka Univ, Inst Adv Cocreat Studies, Suita, Osaka 5650871, Japan; [Ohkubo, Kei] Osaka Univ, Inst Acad Initiat, Suita, Osaka 5650871, Japan; [Fukuzumi, Shunichi] Meijo Univ, Fac Sci & Technol, Tempaku Ku, Nagoya, Aichi 4688502, Japan; [Fukuzumi, Shunichi] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 120750, South Korea
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2019
- URI http://www.dcollection.net/handler/ewha/000000160144
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/acs.jpcc.9b02449
초록/요약
We have successfully constructed hydrogen-bonded supramolecular assemblies based on a diprotonated saddle-distorted porphyrin (H4DPP2+) and redox-active molecules bearing a carboxylate group, such as a Ru-II polypyridyl complex ((RuCOO-)-C-II) that can act as an electron donor and a benzyl viologen derivative (BV2+COO-) that can act as an electron acceptor. Formation of supramolecular assemblies of H4DPP2+ with (RuCOO-)-C-II(HH4DPP2+((RuCOO-)-C-II)(2) and H4DPP2+((RuCOO-)-C-II)(Cl-)) and BV2+COO- (H4DPP2+(BV2+COO-)(2)) was confirmed in acetone by H-1 NMR measurements, CSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics of H4DPP2+((RuCOO-)-C-II)(2) and H4DPP2+(BV2+COO-)(2) was elucidated by femto-, pico-, and nanosecond time-resolved transient absorption spectroscopy. In H4DPP2+((RuCOO-)-C-II)(2), intrasupramolecular photoinduced electron transfer (ET) occurred from the Ru-II center to the singlet excited state of H4DPP2+ to afford an ET state involving one-electron-reduced H4DPP center dot+ and the corresponding one-electron-oxidized Ru-III complex with the lifetime of 150 ps. On the other hand, in the presence of an external electron donor, intermolecular photoinduced ET occurred from an electron donor to the triplet excited state of H4DPP2+(BV2+COO-)(2) to afford H4DPP center dot+, following intrasupramolecular thermal ET proceeded from H4DPP center dot+ to BV2+COO- to form H4DPP2+(BV center dot+COO-)(BV2+COO-) with the lifetime of 1.1 ms. Thus, H4DPP2+ can act as an electron mediator in hydrogen-bonded supramolecular assemblies. This is the first example of porphyrins as a photosensitizer and an electron mediator in hydrogen-bonded ET systems.
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