Nanospheres of copper(iii) 1,2-dicarbomethoxy-1,2-dithiolate and its composite with water soluble carbon nanotubes

Abstract

We report here the synthesis and structural characterization of a new discrete bis-dithiolene complex, [PPh4][Cu(DMED)2] (1; DMED = 1,2-dicarbomethoxy-1,2-dithiolate), involving the reaction between a copper polysulfide precursor with activated acetylene. 1 is stable, showing a sulfur-based radical character, as observed by electronic, EPR and cyclic voltammetric studies. This complex, possessing terminal –COOCH3 groups, forms nanospheres by hydrogen bonding in a mixture of solvents containing water as one of the components. These nanospheres further aggregate with water soluble (carboxylated) carbon nanotubes (wsCNTs). These nano-composites are assisted by hydrogen bonding between the carboxylic acid groups of the wsCNTs and the peripheral –COOCH3 groups of the coordinated dithiolenes of the nanospheres, which is promoted by water molecules. Interaction between the nanospheres on wrapping with wsCNTs, in forming the nano-composites, showed a perturbed EPR signal of the sulfur radical originating from the oxidised dithiolate ligand of the discrete complex 1.