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Issue 11, 2004
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Synthesis, structure, redox, NLO and DNA interaction aspects of [{(L′‴)2RuII}33-L)]3+ and [(L′)2RuII(NC5H4S)]+ [L3− = 1,3,5-triazine-2,4,6-trithiolato, L′‴ = arylazopyridine]

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Abstract

The trinuclear complexes [{(L′‴)2RuII}33-L)](ClO4)3, [1](ClO4)3–[3](ClO4)3 {L = trianionic form of 1,3,5-triazine-2,4,6-trithiol; NpC5H4N[double bond, length as m-dash]Na–C6H4(R), R = H (L′), m-Me (L″), p-Me (L‴)} and the analogous mononuclear complex [(L′)2RuII(NC5H4S)]ClO4 [4]ClO4 were synthesized. Crystal structures of [1](ClO4)3 and [4]ClO4 were determined. [1]3+–[3]3+ exhibit three successive oxidative couples corresponding to RuIIRuIIRuIII ⇌ RuIIRuIIRuII; RuIIRuIIIRuIII ⇌ RuIIRuIIRuIII; RuIIIRuIIIRuIII ⇌ RuIIRuIIIRuIII where the mixed valent states are moderately coupled. The complexes display multiple reductions associated with the azo functions of the ancillary ligands (L′‴). The energy of the RuII-based lowest energy MLCT transitions (533–558 nm) involving the π* level of azoimine chromophore of L′‴ varies depending on the nuclearity as well as substituents in the ligand framework and follows the order: [1]3+ > [2]3+ > [3]3+ > [4]+. The complexes exhibit reasonably high third-order non-linear optical properties with γ = (0.90–2.45) × 10−29 esu. The interactions of the trinuclear complexes [{(L′)2RuII}33-L)]3+ [1]3+, [{(bpy)2RuII}33-L)]3+ [5]3+ and [{(phen)2RuII}33-L)]3+ [6]3+ (bpy = 2,2′-bipyridine and phen = 1,10-phenanthroline) with the circular and linear forms of p-Bluescript DNA show reduced ethidium bromide fluorescence on gel electrophoresis.

Graphical abstract: Synthesis, structure, redox, NLO and DNA interaction aspects of [{(L′–‴)2RuII}3(μ3-L)]3+ and [(L′)2RuII(NC5H4S−)]+ [L3− = 1,3,5-triazine-2,4,6-trithiolato, L′–‴ = arylazopyridine]

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Publication details

The article was received on 03 Mar 2004, accepted on 21 Apr 2004 and first published on 06 May 2004


Article type: Paper
DOI: 10.1039/B403332A
Citation: Dalton Trans., 2004,0, 1752-1760
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    Synthesis, structure, redox, NLO and DNA interaction aspects of [{(L′‴)2RuII}33-L)]3+ and [(L′)2RuII(NC5H4S)]+ [L3− = 1,3,5-triazine-2,4,6-trithiolato, L′‴ = arylazopyridine]

    S. Kar, B. Pradhan, R. K. Sinha, T. Kundu, P. Kodgire, K. K. Rao, V. G. Puranik and G. K. Lahiri, Dalton Trans., 2004, 0, 1752
    DOI: 10.1039/B403332A

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