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• W2045552677 abstract "The reaction of Ru(trpy)Cl(3) (trpy = 2,2':6',2-terpyridine) with the pyridine-based imine function N(p)C(5)H(4)-CH=N(i)-NH-C(6)H(5) (L), incorporating an NH spacer between the imine nitrogen (N(i)) and the pendant phenyl ring, in ethanol medium followed by chromatographic work up on a neutral alumina column using CH(3)CN/CH(2)Cl(2) (1:4) as eluent, results in complexes of the types [Ru(trpy)(L')](ClO(4))(2) (1) and [Ru(trpy)(L)Cl]ClO(4) (2). Although the identity of the free ligand (L) has been retained in complex 2, the preformed imine-based potentially bidentate ligand (L) has been selectively transformed into a new class of unusual imine-amidine-based tridentate ligand, N(p)C(5)H(4)-CH=N(i)-N(C(6)H(5))C(CH(3))=N(a)H (L'), in 1. The single-crystal X-ray structures of the free ligand (L) and both complexes 1 and 2 have been determined. In 2, the sixth coordination site, that is, the Cl(-) function, is cis to the pyridine nitrogen (N(p)) of L which in turn places the NH spacer away from the Ru-Cl bond, whereas, in 1, the corresponding sixth position, that is, the Ru-N(a) (amidine) bond, is trans to the pyridine nitrogen (N(p)) of L'. The trans configuration of N(a) with respect to the N(p) of L' in 1 provides the basis for the selective L --> L' transformation in 1. The complexes exhibit strong Ru(II) --> pi* (trpy) MLCT transitions in the visible region and intraligand transitions in the UV region. The lowest energy MLCT band at 510 nm for 2 has been substantially blue-shifted to 478 nm in the case of 1. The reversible Ru(III)-Ru(II) couples for 1 and 2 have been observed at 0.80 and 0.59 V versus SCE, respectively. The complexes are weakly luminescent at 77 K, exhibiting emissions at lambda(max), 598 nm [quantum yield (Phi) = 0.43 x 10(-2)] and 574 nm (Phi = 0.28 x 10(-2)) for 1 and 2, respectively." @default.
• W2045552677 created "2016-06-24" @default.
• W2045552677 creator A5054766972 @default.
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• W2045552677 date "2002-10-04" @default.
• W2045552677 modified "2023-10-10" @default.
• W2045552677 title "Example of Highly Stereoregulated Ruthenium Amidine Complex Formation: Synthesis, Crystal Structures, and Spectral and Redox Properties of the Complexes [Ru^II(trpy){NC₅H₄CHNN(C₆H₅)C(CH₃)NH}](ClO₄)₂ (<b>1</b>) and [Ru^II(trpy)(NC₅H₄CHNNHC₆H₅)Cl]ClO₄ (<b>2</b>) (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine)" @default.
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• W2045552677 doi "https://doi.org/10.1021/ic020351+" @default.
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