Synthesis, structure, redox, NLO and DNA interaction aspects of [((L'-'")2RuII)3(mu3-L)]3+ and...

The trinuclear complexes [(L'-'")2RuII)3(mu3-L)](ClO4)3, [1] (ClO4)3-[3](ClO4)3 (L = trianionic form of 1,3,5-triazine-2,4,6-trithiol; N(p)C(5)H(4)N=N(a)-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 Ru(II)Ru(II)Ru(III)<==>Ru(II)Ru(II)Ru(II); Ru(II)Ru(III)Ru(III)<==>Ru(II)Ru(II)Ru(III); Ru(III)Ru(III)Ru(III)<==>Ru(II)Ru(III)Ru(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 Ru(II)-based lowest energy MLCT transitions (533-558 nm) involving the pi* 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 gamma= (0.90-2.45) [times] 10(-29) esu. The interactions of the trinuclear complexes [((L')2RuII)3(mu3-L)]3+[1]3+, [((bpy)2RuII)3((mu3-L)]3+[5]3+ and [((phen)2RuII)3((mu3)-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.