A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies
- Wataru SuzukiWataru SuzukiDepartment of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Wataru Suzuki,
- Hiroaki KotaniHiroaki KotaniDepartment of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Hiroaki Kotani,
- Tomoya IshizukaTomoya IshizukaDepartment of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Tomoya Ishizuka,
- Masaki KawanoMasaki KawanoDepartment of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, JapanMore by Masaki Kawano,
- Hayato SakaiHayato SakaiDepartment of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, JapanMore by Hayato Sakai,
- Taku HasobeTaku HasobeDepartment of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, JapanMore by Taku Hasobe,
- Kei OhkuboKei OhkuboInstitute for Advanced Co-Creation Studies and Institute for Academic Initiatives, Osaka University, Suita, Osaka 565-0871, JapanMore by Kei Ohkubo,
- Shunichi FukuzumiShunichi FukuzumiFaculty of Science and Technology, Meijo University, Tempaku, Nagoya, Aichi 468-8502, JapanDepartment of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, South KoreaMore by Shunichi Fukuzumi, and
- Takahiko Kojima*Takahiko Kojima*E-mail: [email protected]Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Takahiko Kojima
Abstract
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 RuII polypyridyl complex (RuIICOO–) 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 RuIICOO– (H4DPP2+(RuIICOO–)2 and H4DPP2+(RuIICOO–)(Cl–)) and BV2+COO– (H4DPP2+(BV2+COO–)2) was confirmed in acetone by 1H NMR measurements, CSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics of H4DPP2+(RuIICOO–)2 and H4DPP2+(BV2+COO–)2 was elucidated by femto-, pico-, and nanosecond time-resolved transient absorption spectroscopy. In H4DPP2+(RuIICOO–)2, intrasupramolecular photoinduced electron transfer (ET) occurred from the RuII center to the singlet excited state of H4DPP2+ to afford an ET state involving one-electron-reduced H4DPP•+ and the corresponding one-electron-oxidized RuIII 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•+, following intrasupramolecular thermal ET proceeded from H4DPP•+ to BV2+COO– to form H4DPP2+(BV•+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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