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论文类型：期刊论文

发表时间：2012-04-01

发表刊物：CHEMISTRY-A EUROPEAN JOURNAL

收录刊物：SCIE、EI、PubMed、Scopus

卷号：18

期号：16

页面范围：4953-4964

ISSN号：0947-6539

关键字：coumarin; light-harvesting; phosphorescence; photochemistry; ruthenium

摘要：RuIIbis-pyridine complexes typically absorb below 450 nm in the UV spectrum and their molar extinction coefficients are only moderate (e<16?000?M-1?cm-1). Thus, RuIIpolyimine complexes that show intense visible-light absorptions are of great interest. However, no effective light-harvesting ruthenium(II)/organic chromophore arrays have been reported. Herein, we report the first visible-light-harvesting RuIIcoumarin arrays, which absorb at 475 nm (e up to 63?300?M-1?cm-1, 4-fold higher than typical RuIIpolyimine complexes). The donor excited state in these arrays is efficiently converted into an acceptor excited state (i.e., efficient energy-transfer) without losses in the phosphorescence quantum yield of the acceptor. Based on steady-state and time-resolved spectroscopy and DFT calculations, we proposed a general rule for the design of RuIIpolypyridinechromophore light-harvesting arrays, which states that the 1IL energy level of the ligand must be close to the respective energy level of the metal-to-ligand charge-transfer (MLCT) states. Lower energy levels of 1IL/3IL than the corresponding 1MLCT/3MLCT states frustrate the cascade energy-transfer process and, as a result, the harvested light energy cannot be efficiently transferred to the acceptor. We have also demonstrated that the light-harvesting effect can be used to improve the upconversion quantum yield to 15.2?% (with 9,10-diphenylanthracene as a triplet-acceptor/annihilator), compared to the parent complex without the coumarin subunit, which showed an upconversion quantum yield of only 0.95?%.