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• W2032177890 abstract "A series of chromophore−quencher complexes, trans-[Ru(bpy)2(pya)(pyb)]n+ (bpy = 2,2‘-bipyridyl; pya, pyb = substituted pyridyl ligands; n = 2−4) have been prepared and characterized. These contain combinations of the electron donor PTZ in py-PTZ (py-PTZ = 10-(4-picolyl)phenothiazine) and the electron acceptors MQ+ (1-methyl-4,4‘-bipyridinium cation), py-AQ (4-((((9,10-anthraquinon-2-yl)carbonyl)amino)methyl)pyridine), and py-MPAA (N-(4-pyridyl)-β-(1-methylpyridinium-3-yl)acrylamide cation), and 4-ethylpyridine (4-Etpy). The asymmetrical complexes (pya ≠ pyb) are synthesized by using the precursor trans-[Ru(bpy)2(DMSO)2](CF3SO3)2·0.5H2O, which is converted into trans-[Ru(bpy)2(py-PTZ)(DMSO)](CF3SO3)2·0.5H2O (1) by reaction with py-PTZ in DMSO/acetone at room temperature. 1 is treated with LiCl in aqueous DMF at 105 °C to prepare trans-[RuCl(bpy)2(py-PTZ)]CF3SO3·H2O (2). 2 is converted into the derivatives trans-[Ru(bpy)2(py-PTZ)(4-Etpy)](PF6)2·0.5H2O (5), trans-[Ru(bpy)2(py-PTZ)(MQ+)](PF6)3 (7), trans-[Ru(bpy)2(py-PTZ)(py-AQ)](PF6)2·H2O (9), and trans-[Ru(bpy)2(py-PTZ)(py-MPAA)](PF6)3·H2O (11) by chloride abstraction at room temperature in the presence of 4-Etpy, [MQ](PF6), py-AQ, and [py-MPAA](PF6), respectively. The salts trans-[Ru(bpy)2(4-Etpy)(MQ+)](PF6)3·H2O (6), trans-[Ru(bpy)2(4-Etpy)(py-AQ)](PF6)2 (8), and trans-[Ru(bpy)2(4-Etpy)(py-MPAA)](PF6)3 (10) are synthesized by chloride abstraction from trans-[RuCl(bpy)2(4-Etpy)]PF6·H2O in the presence of [MQ](PF6), py-AQ, or [py-MPAA](PF6). The symmetrical complexes trans-[Ru(bpy)2(MQ+)2](PF6)4·3H2O (3) and trans-[Ru(bpy)2(py-PTZ)2](PF6)2·H2O (4) are synthesized by reaction of trans-[Ru(bpy)2(H2O)2](CF3SO3)2 with an excess of the appropriate ligand in DMF at 100 °C. Visible light irradiation of these complexes at room temperature leads to photochemical decomposition. At lower temperatures (<200 K), emission typical of RuIII−bpy•- (and RuIII−MQ•) MLCT states is observed. The appearance of a thermally activated decay pathway above 150 K signals the presence of a crossing to a photochemically reactive ligand-field state. As a result, significant formation of redox-separated states by electron transfer is not observed for the redox triads trans-[Ru(bpy)2(py-PTZ)(X)]n+ (X = py-AQ, n = 2; X = py-MPAA or MQ+, n = 3). Nonetheless, the results obtained have important implications for the stereochemical design of Ru(II)-based chromophore−quencher complexes." @default.
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• W2032177890 date "1996-01-01" @default.
• W2032177890 modified "2023-10-17" @default.
• W2032177890 title "<i>trans</i>-Chromophore−Quencher Complexes Based on Ruthenium(II)" @default.
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• W2032177890 doi "https://doi.org/10.1021/ic9515463" @default.
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