Intramolecular Luminescence Quenching in Amino Acid Bridged Ruthenium(II)-Copper(II) Complexes with Negligible Ground-State Coupling
作者:Bernd Geißer、Ralf Alsfasser
DOI:10.1002/(sici)1099-0682(199807)1998:7<957::aid-ejic957>3.0.co;2-6
日期:1998.7
appreciable ground-state coupling between ruthenium(II) and copper(II). However, the luminescence of 1b–4b is significantly quenched compared to that of the parent compounds 1a–4a. Quenching was found to proceed only intramolecularly and to be most efficient in 1b with the shortest alkyl spacer. Equilibrium constants for the formation of 1b–4b were determined from luminescence titrations of the respective ruthenium-substituted
一系列异双金属配合物 [Ru(bipy)2}m-AACu(phen)(H2O)}](PF6)3 (m-AA = Nω-(4-carbonyl-4′-methyl-2,2 '-联吡啶基)-L-α,ω-二氨基酸;二氨基酸 (AA): 1b, L-2,3-二氨基丙酸; 2b, L-2,4-二氨基丁酸; 3b, L-鸟氨酸, 4b, L-赖氨酸)已从 2,2'-联吡啶钌 (II) 取代的氨基酸 [Ru(bipy)2}m-AA-αN-tBoc]2+ (αN-tBoc-1a– 4a,αN-tBoc = Nα-叔丁氧基羰基)。1b-4b 中的金属中心由绝缘的烷基链桥接。因此,光谱和电化学研究证实了钌 (II) 和铜 (II) 之间不存在任何明显的基态耦合。然而,与母体化合物 1a-4a 的发光相比,1b-4b 的发光显着淬灭。发现淬火仅在分子内进行,并且在具有最短烷基间隔基的 1b 中最有效。1b-4b