A Diprotonated Porphyrin as an Electron Mediator in\nPhotoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies

Wataru Suzuki (423403); Hiroaki Kotani (1415575); Tomoya Ishizuka (1415599); Masaki Kawano (1414144); Hayato Sakai (1581946); Taku Hasobe (1581955); Kei Ohkubo (1326819); Shunichi Fukuzumi (1326822); Takahiko Kojima (1415593)

JOURNAL ARTICLE

A Diprotonated Porphyrin as an Electron Mediator in\nPhotoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies

Wataru Suzuki (423403)Hiroaki Kotani (1415575)Tomoya Ishizuka (1415599)Masaki Kawano (1414144)Hayato Sakai (1581946)Taku Hasobe (1581955)Kei Ohkubo (1326819)Shunichi Fukuzumi (1326822)Takahiko Kojima (1415593)

Year: 2019 Journal: OPAL (Open@LaTrobe) (La Trobe University) Publisher: La Trobe University

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Abstract

We have successfully\nconstructed hydrogen-bonded supramolecular\nassemblies based on a diprotonated saddle-distorted porphyrin (H4DPP2+) and redox-active molecules bearing a carboxylate group, such\nas a RuII polypyridyl complex (RuIICOO–)\nthat can act as an electron donor and a benzyl viologen derivative\n(BV2+COO–) that can act as an electron acceptor. Formation\nof 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,\nCSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics\nof H4DPP2+(RuIICOO–)2 and H4DPP2+(BV2+COO–)2 was elucidated by femto-, pico-, and nanosecond\ntime-resolved transient absorption spectroscopy. In H4DPP2+(RuIICOO–)2, intrasupramolecular\nphotoinduced electron transfer (ET) occurred from the RuII center to the singlet excited state of H4DPP2+ to afford\nan ET state involving one-electron-reduced H4DPP•+ and\nthe corresponding one-electron-oxidized RuIII complex with\nthe lifetime of 150 ps. On the other hand, in the presence of an external\nelectron donor, intermolecular photoinduced ET occurred from an electron\ndonor 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\nof 1.1 ms. Thus, H4DPP2+ can act as an electron mediator in hydrogen-bonded\nsupramolecular assemblies. This is the first example of porphyrins\nas a photosensitizer and an electron mediator in hydrogen-bonded ET\nsystems.

Keywords:

Porphyrin Supramolecular chemistry Electron transfer Excited state Intermolecular force Photosensitizer Viologen Triplet state Carboxylate

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A Diprotonated Porphyrin as an Electron Mediator in\nPhotoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies

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