Enhanced Photocatalysis of Rhenium(I) Complex by Light-Harvesting Periodic Mesoporous Organosilica

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• 作者：Hiroyuki Takeda ; Masataka Ohashi ; Takao Tani ; Osamu Ishitani ; Shinji Inagaki
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：May 17, 2010
• 年：2010
• 卷：49
• 期：10
• 页码：4554-4559
• 全文大小：834K
• 年卷期：v.49,no.10(May 17, 2010)
• ISSN：1520-510X

文摘

This paper describes a new conceptual design for enhancement of photocatalytic CO₂ reduction of a rhenium(I) complex by light harvesting of periodic mesoporous organosilica (PMO). Mesoporous biphenyl-silica (Bp-PMO) anchoring fac-[Re^I(bpy)(CO)₃(PPh₃)]⁺(OTf)⁻ (bpy =2,2′-bipyridine; OTf = CF₃SO₃) in the mesochannels was synthesized by co-condensation of two organosilane precursors, 4,4′-bis(triethoxysilyl)biphenyl and 4-[4-{3-(trimethoxysilyl)propylsulfanyl}butyl]-4′-methyl-2,2′-bipyridine in the presence of a template surfactant, followed by coordination of a rhenium precursor, [Re^I(CO)₅(PPh₃)]⁺(OTf)⁻ to the bipyridine ligand in the mesochannels. The 280 nm light was effectively absorbed by the biphenyl groups in Bp-PMO, and the excited energy was funneled into the Re complex by resonance energy transfer, which enhanced photocatalytic CO evolution from CO₂ by a factor of 4.4 compared with direct excitation of the Re complex. Bp-PMO had an additional merit to protect the Re complex against a decomposition by UV irradiation. These results demonstrate the potential of PMOs as a light-harvesting antenna for designing various photoreaction systems, mimicking the natural photosynthesis.