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

Sanjib Kar, Biswajit Pradhan, Rajeev Kumar Sinha, Tapanendu Kundu, Prashant Kodgire, K. Krishnamurthy Rao, Vedavati G. Puranik, Goutam Kumar Lahiri

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Abstract

The trinuclear complexes [{(L′-″′) 2RuII}33-L)](ClCO 4)3, (ClO4)3 - (ClO 4)3 {L = trianionic form of 1,3,5-triazine-2,4,6-trithiol; NpC5H4N=Na - C6H 4(R), R= H (L′), m-Me (L″),p-Me (L″′)} and the analogous mononuclear complex [(L′)2RuII(NC 5H4S-)]ClO4 ClO4 were synthesized. Crystal structures of (ClO4)3 and ClO 4 were determined. 3-3- exhibit three successive oxidative couples corresponding to RuIIR IIRIII⇌ RiIIRiIIRu II; RuIIRuIIIRuIII ⇌ Ru IIRuIIRuIII; RuIIIRu IIIRuIII ⇌ RuIIRuIIIRu III 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: 3+ > 3+ > 3+ > +. 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- 3+, [{(bpy)2RuII} 33-L)]3- 3+ and [{(phen) 2RuII}33-L)]3+ 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.

Original languageEnglish
Pages (from-to)1752-1760
Number of pages9
JournalDalton Transactions
Issue number11
Publication statusPublished - 07-06-2004

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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