Synthesis, molecular structure and supramolecular chemistry of a new nickel-quinoxaline dithiolate system [Bu < inf > 4 < /inf > N] < inf > 2 < /inf > [Ni(6,7-qdt) < inf > 2 < /inf > ] (6,7-qdt = quinoxaline-6,7-dithiolate) and comparison of its electronic and electrochemical properties with those of [Bu < inf > 4 < /inf > N] < inf > 2 < /inf > [Ni(qdt) < inf > 2 < /inf > ] (qdt = quinoxaline-2,3-dithiolate)

Abstract

The new nickel bis(dithiolene) complex [Bu4N] 2[Ni(6,7-qdt)2] (1) (6,7-qdt = quinoxaline-6,7-dithiolate) has been synthesized, starting from quinoxaline-6,7-dithiol, nickel chloride and tetrabutylammonium bromide in methanol. Compound 1 crystallizes in P2 1/c space group (monoclinic system). Its crystal structure has been characterized by interesting C-H⋯S and C-H⋯N weak interactions resulting in a three dimensional supramolecular network. Complex 1 shows solvent sensitive absorption band (broad feature) in the visible region, which is attributed to charge transfer (CT) transition involving electronic excitation from a HOMO that is a mixture of dithiolate (π) and metal (d) orbital character to a LUMO which is a π* orbital of the dithiolate. This CT transition absorbs at low energy region in comparison to the CT band of the [Bu4N]2[Ni(qdt)2] in the visible region. Interestingly, compound 1 undergoes reversible oxidation at very low oxidation potential (E1/2 = + 0.12 V vs Ag/AgCl) compared to that of [Ni(qdt)2]2- (E1/2 = + 0.41 V vs Ag/AgCl) in MeOH solutions. © 2011 Elsevier B.V.