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论文类型：期刊论文

发表时间：2018-07-07

发表刊物：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录刊物：SCIE

卷号：20

期号：25

页面范围：17504-17516

ISSN号：1463-9076

摘要：A bipyridine ruthenium(ii) complex (Ru-1) with a flavin moiety connected to one of the bipyridine ligands via an acetylene bond was designed and synthesized, and its photophysical properties were investigated. Compared with the tris(bipyridine) Ru(ii) complex (Ru-0), which has an extinction coefficient epsilon = 1.36 x 10(4) M-1 cm(-1) at 453 nm, the introduction of the flavin moiety endows Ru-1 with strong absorption in the visible range (epsilon = 2.34 x 10(4) M-1 cm(-1) at 456 nm). Furthermore, Ru-1 exhibits phosphorescence ((em) = 643 nm, phi(P) = 1%, (P) = 1.32 s at 293 K and 4.53 s at 77 K). We propose that the emission of Ru-1 originates from the low lying triplet excited state of (IL)-I-3 according to the time-resolved transient difference absorption spectra, the calculated T-1 spin density and the T-1 thermo-vibration modes localized on the flavin-decorated bipyridine ligand. This is the first time that the phosphorescence of flavin was observed within Ru(ii) complexes. Consequently, Ru-1 was used for triplet-triplet annihilation upconversion, showing a reasonable quantum yield of 0.7% with respect to the phosphorescence quantum yield of 1%. These findings pave the way for the rational design of phosphorescence transition metal complexes. Also, further approaches that may improve the performance of flavin-decorated Ru(ii) bipyridine complexes are proposed.