Eilatin complexes of ruthenium and osmium. synthesis, electrochemical behavior, and near-IR luminescence

被引:45
作者
Bergman, SD
Gut, D
Kol, M [1 ]
Sabatini, C
Barbieri, A
Barigelletti, F
机构
[1] Tel Aviv Univ, Sch Chem, Raymond & Beverly Sackler Fac Exact Sci, IL-69978 Tel Aviv, Israel
[2] CNR, ISOF, I-40129 Bologna, Italy
关键词
D O I
10.1021/ic051022v
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis and characterization of new Ru(II) and Os(II) complexes of the ligand eilatin (1) are described. The new complexes [Ru(bpy)(eil)(2)](2+) (2), [Ru(eil)(3)](2+) (3), and [Os(eil)(3)](2+) (4) (bpy = 2,2'-bipyridine; eil = eilatin) were synthesized and characterized by NMR, fast atom bombardment mass spectrometry, and elemental analysis, In the series of complexes [Ru(bpy)(x)(eil)(y)](2+) (x + y = 3), the effect of sequential substitution of eil for bpy on the electrochemical and photophysical properties was examined. The absorption spectra of the complexes exhibit several bpy- and eil-associated pi-pi* and metal-to-ligand charge-transfer (MLCT) transitions in the visible region (400-600 nm), whose energy and relative intensity depend on the number of ligands bound to the metal center (x and y). On going from [Ru(bpy)(2)(eil)](2+) (5) to 2 to 3, the d(pi)(Ru) -> pi*(eil) MLCT transition undergoes a red shift from 583 to 591 to 599 nm, respectively. Electrochemical measurements performed in dimethyl sulfoxide reveal several ligand-based reduction processes, where each eil ligand can accept up to two electrons at potentials that are significantly anodically shifted (by ca. 1 V) with respect to the bpy ligands. The complexes exhibit near-IR emission (900-1100 nm) of typical (MLCT)-M-3 character, both at room temperature and at 77 K. Along the series 5, 2, and 3, upon substitution of eil for bpy, the emission maxima undergo a blue shift and the quantum yields and lifetimes increase. The radiative and nonradiative processes that contribute to deactivation of the excited level are discussed in detail.
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页码:7943 / 7950
页数:8
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