TY - JOUR
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
N1 - Funding Information:
This work was supported by Grant-in-Aid (17H03027 and 18J12184) from the Japan Society of Promotion of Science (JSPS, MEXT) of Japan. Financial support through CREST (JST) is also appreciated (JPMJCR16P1).
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/5/9
Y1 - 2019/5/9
N2 - 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.
AB - 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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U2 - 10.1021/acs.jpcc.9b02449
DO - 10.1021/acs.jpcc.9b02449
M3 - Article
AN - SCOPUS:85065620917
SN - 1932-7447
VL - 123
SP - 11529
EP - 11538
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 18
ER -