This article demonstrates the stabilization of ground-and redoxinduced metal-to-ligand charge transfer excited states on coordination of azocoupled bmpd(L4) [bmpd = (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene; L4 = −N�N−] to the electron-rich {Ru(acac) 2 } (acac = acetylacetonate) unit in mononuclear Ru II (acac) 2 (L4) (1) and diastereomeric dinuclear (acac) 2 Ru 2.5 (μ-L4 •− )Ru 2.5 (acac) 2 [rac, ΔΔ/ΛΛ (2a)/meso, ΔΛ (2b)] complexes, respectively. It also develops further one-step intramolecular electron transfer induced L4On the contrary, under identical reaction conditions electronically and sterically permuted bimpd [L5, (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene)] delivered mononuclear Ru II (acac) 2 (L5) (3) as an exclusive product. Further, the generation of unprecedented heterotrinuclear complex [(acac) 2 Ru II (μ-L4)Ag I (μ-L4)Ru II (acac) 2 ]ClO 4 ([4]ClO 4 ) involving unreduced L4 via the reaction of 1 and AgClO 4 revealed the absence of any inner-sphere electron transfer (IET) as in precursor 1, which in turn reaffirmed an IET (at the interface of electron-rich Ru(acac) 2 and acceptor L4) mediated stabilization of 2. Structural authentication of the complexes with special reference to the tunable azo distance (N�N, N−N •− , N−N 2− ) of L and their spectro-electrochemical events in accessible redox states including the reversible electron reservoir feature of 2 → 2 + /2 + → 2 were evaluated in conjunction with density functional theory/time-dependent density functional theory calculations. The varying extent of IET as a function of heteroaromatics appended to the azo group of L (L1 = abpy = 2,2′-azobipyridine, L2 = abbt = 2,2′-azobis(benzothiazole), L3 = abim = azobis(1-methylbenzimidazole), L4 and L5, Schemes 1 & 2) in the Ru(acac) 2 -derived respective molecular setup has been addressed.
The article dealt with the structural and electronic forms of hitherto unexplored L2‒ (H2L=2,5-bis(2-hydroxyphenyl)thiazolo-[5,4-d]thiazole) bridged analogous diruthenium [{(AL1/AL2)2 RuII}2(-L2)]2+ [1](ClO4)2/[2](ClO4)2 and diosmium [{(AL1/AL2)2OsII}2(-L2)]2+ [3](PF6)2/[4](ClO4)2 complexes as a function of moderate...
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