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Effects of phosphonate ester groups attached on a heteroleptic Ir(III) photosensitizer

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Title: Effects of phosphonate ester groups attached on a heteroleptic Ir(III) photosensitizer
Authors: Kobayashi, Atsushi Browse this author →KAKEN DB
Watanabe, Shuhei Browse this author
Ebina, Masanori Browse this author
Yoshida, Masaki Browse this author →KAKEN DB
Kato, Masako Browse this author →KAKEN DB
Keywords: Photocatalyst
Artificial photosynthesis
Cyclometalated Ir(III) complex
Issue Date: 1-Oct-2017
Publisher: Elsevier
Journal Title: Journal of photochemistry and photobiology a-chemistry
Volume: 347
Start Page: 9
End Page: 16
Publisher DOI: 10.1016/j.jphotochem.2017.06.042
Abstract: Two heteroleptic Ir(III) complexes bearing two diethyl phosphonate groups, [Ir(ppy-PE)(2)(bpy)(PF6) and [Ir(ppy)(2)(bpy-dPE)](PF6) (1pPE and 1bPE; Hppy = 2-phenylpyridine, Hppy-PE =4-(diethylphosphonomethyl)-2-phenylpyridine, bpy = 2,2'-bipyridine, bpy-dPE=4,4'-bis(diethylphosphonomethyl)-2,2'bipyridine), were successfully synthesized, and their photophysical properties were investigated by UV-vis absorption and emission spectroscopic and electrochemical measurements. Both IpPE and IbPE complexes exhibited similar IJV-vis absorption and emission spectra and cyclic voltammograms as those of nonmodified complex [Ir(ppy)2(bpy)](PF6) (1), indicating the suitability for photocatalytic H-2 evolution reaction. (MLCT)-M-3 emissions of both IbPE and 1pPE were quenched by electron transfer from triethylamine (TEA) sacrificial electron donor, but the quenching rate of IpPE was lower than that of nonmodified complex 1 and 1bPE. In contrast, the quenching rate of IbPE by an electron-accepting [Co (bpy)(3)](2+) moiety was slightly lower than 1 or IpPE. These results suggest that the two diethylphosphonate ester groups regulate the direction of photoinduced electron-transfer reaction at the (MLCT)-M-3 excited state due to their steric bulkiness. In addition, the photocatalytic activity for H-2 evolution in the presence of K2PtC14 precatalyst clearly showed remarkably extended longevity for both IpPE and 1bPE compared to that of 1, indicating that the two diethyl phosphonate groups attached on IpPE and IbPE also play an important role in the extended longevity of H-2-evolution activity of in-situ generated Pt colloidal catalyst from K2PtC14. The deactivation pathway of IpPE and 1bPE during photo H-2 evolution reaction is mainly due to the substitution of the bpy-type ligand by CH3CN solvent of the one electron reduced Ir(II) species like the non-substituted complex 1. (C) 2017 Elsevier B.V. All rights reserved.
Rights: ©2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license
Type: article (author version)
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 小林 厚志

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