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

Wataru Suzuki, Hiroaki Kotani, Tomoya Ishizuka, Masaki Kawano, Hayato Sakai, Taku Hasobe, Kei Ohkubo, Shunichi Fukuzumi, Takahiko Kojima

Research output: Contribution to journalArticle

Abstract

We have successfully constructed hydrogen-bonded supramolecular assemblies based on a diprotonated saddle-distorted porphyrin (H 4 DPP 2+ ) and redox-active molecules bearing a carboxylate group, such as a Ru II polypyridyl complex (Ru II COO - ) that can act as an electron donor and a benzyl viologen derivative (BV 2+ COO - ) that can act as an electron acceptor. Formation of supramolecular assemblies of H 4 DPP 2+ with Ru II COO - (H 4 DPP 2+ (Ru II COO - ) 2 and H 4 DPP 2+ (Ru II COO - )(Cl - )) and BV 2+ COO - (H 4 DPP 2+ (BV 2+ COO - ) 2 ) was confirmed in acetone by 1 H NMR measurements, CSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics of H 4 DPP 2+ (Ru II COO - ) 2 and H 4 DPP 2+ (BV 2+ COO - ) 2 was elucidated by femto-, pico-, and nanosecond time-resolved transient absorption spectroscopy. In H 4 DPP 2+ (Ru II COO - ) 2 , intrasupramolecular photoinduced electron transfer (ET) occurred from the Ru II center to the singlet excited state of H 4 DPP 2+ to afford an ET state involving one-electron-reduced H 4 DPP •+ 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 H 4 DPP 2+ (BV 2+ COO - ) 2 to afford H 4 DPP •+ , following intrasupramolecular thermal ET proceeded from H 4 DPP •+ to BV 2+ COO - to form H 4 DPP 2+ (BV •+ COO - )(BV 2+ COO - ) with the lifetime of 1.1 ms. Thus, H 4 DPP 2+ 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.

Original languageEnglish
Pages (from-to)11529-11538
Number of pages10
JournalJournal of Physical Chemistry C
Volume123
Issue number18
DOIs
Publication statusPublished - 2019 May 9

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Porphyrins
porphyrins
assemblies
Hydrogen
electron transfer
Electrons
hydrogen
electrons
life (durability)
Excited states
carboxyl radical
saddles
Bearings (structural)
Benzyl Viologen
carboxylates
acetone
excitation
absorption spectroscopy
Photosensitizers
Photosensitizing Agents

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies. / Suzuki, Wataru; Kotani, Hiroaki; Ishizuka, Tomoya; Kawano, Masaki; Sakai, Hayato; Hasobe, Taku; Ohkubo, Kei; Fukuzumi, Shunichi; Kojima, Takahiko.

In: Journal of Physical Chemistry C, Vol. 123, No. 18, 09.05.2019, p. 11529-11538.

Research output: Contribution to journalArticle

Suzuki, Wataru ; Kotani, Hiroaki ; Ishizuka, Tomoya ; Kawano, Masaki ; Sakai, Hayato ; Hasobe, Taku ; Ohkubo, Kei ; Fukuzumi, Shunichi ; Kojima, Takahiko. / A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies. In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 18. pp. 11529-11538.
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abstract = "We have successfully constructed hydrogen-bonded supramolecular assemblies based on a diprotonated saddle-distorted porphyrin (H 4 DPP 2+ ) and redox-active molecules bearing a carboxylate group, such as a Ru II polypyridyl complex (Ru II COO - ) that can act as an electron donor and a benzyl viologen derivative (BV 2+ COO - ) that can act as an electron acceptor. Formation of supramolecular assemblies of H 4 DPP 2+ with Ru II COO - (H 4 DPP 2+ (Ru II COO - ) 2 and H 4 DPP 2+ (Ru II COO - )(Cl - )) and BV 2+ COO - (H 4 DPP 2+ (BV 2+ COO - ) 2 ) was confirmed in acetone by 1 H NMR measurements, CSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics of H 4 DPP 2+ (Ru II COO - ) 2 and H 4 DPP 2+ (BV 2+ COO - ) 2 was elucidated by femto-, pico-, and nanosecond time-resolved transient absorption spectroscopy. In H 4 DPP 2+ (Ru II COO - ) 2 , intrasupramolecular photoinduced electron transfer (ET) occurred from the Ru II center to the singlet excited state of H 4 DPP 2+ to afford an ET state involving one-electron-reduced H 4 DPP •+ 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 H 4 DPP 2+ (BV 2+ COO - ) 2 to afford H 4 DPP •+ , following intrasupramolecular thermal ET proceeded from H 4 DPP •+ to BV 2+ COO - to form H 4 DPP 2+ (BV •+ COO - )(BV 2+ COO - ) with the lifetime of 1.1 ms. Thus, H 4 DPP 2+ 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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T1 - A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies

AU - Suzuki, Wataru

AU - Kotani, Hiroaki

AU - Ishizuka, Tomoya

AU - Kawano, Masaki

AU - Sakai, Hayato

AU - Hasobe, Taku

AU - Ohkubo, Kei

AU - Fukuzumi, Shunichi

AU - Kojima, Takahiko

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N2 - We have successfully constructed hydrogen-bonded supramolecular assemblies based on a diprotonated saddle-distorted porphyrin (H 4 DPP 2+ ) and redox-active molecules bearing a carboxylate group, such as a Ru II polypyridyl complex (Ru II COO - ) that can act as an electron donor and a benzyl viologen derivative (BV 2+ COO - ) that can act as an electron acceptor. Formation of supramolecular assemblies of H 4 DPP 2+ with Ru II COO - (H 4 DPP 2+ (Ru II COO - ) 2 and H 4 DPP 2+ (Ru II COO - )(Cl - )) and BV 2+ COO - (H 4 DPP 2+ (BV 2+ COO - ) 2 ) was confirmed in acetone by 1 H NMR measurements, CSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics of H 4 DPP 2+ (Ru II COO - ) 2 and H 4 DPP 2+ (BV 2+ COO - ) 2 was elucidated by femto-, pico-, and nanosecond time-resolved transient absorption spectroscopy. In H 4 DPP 2+ (Ru II COO - ) 2 , intrasupramolecular photoinduced electron transfer (ET) occurred from the Ru II center to the singlet excited state of H 4 DPP 2+ to afford an ET state involving one-electron-reduced H 4 DPP •+ 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 H 4 DPP 2+ (BV 2+ COO - ) 2 to afford H 4 DPP •+ , following intrasupramolecular thermal ET proceeded from H 4 DPP •+ to BV 2+ COO - to form H 4 DPP 2+ (BV •+ COO - )(BV 2+ COO - ) with the lifetime of 1.1 ms. Thus, H 4 DPP 2+ 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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