Electronic and Magnetic Properties of Infinite 1D Chains of Paddlewheel Carboxylates M2(COOR)4 (M = Mo, W, Ru, Rh, Ir, Cu)

Dinuclear complexes of transition metals bridged by four carboxylate-groups are examples of stable atomic configurations serving as fundamental building blocks of catalysts and prototypical molecular electronic devices. The electronic structure and magnetic properties of many molecular tetracarboxylate complexes were meticulously studied; however, the properties of the one-dimensional (1D) polymeric chain of associated tetracarboxylates have so far evaded much attention. Using periodic density-functional theory calculations, we analyze the electronic structure of condensed tetracarboxylates Mo­(II), W­(II), Ru­(II), Rh­(II), Ir­(II), and Cu­(II). The relationship between crystal structure of the polymerized tetracarboxylates and the electronic properties of the metal–metal bond in the M24+ core is studied. The electronic effects emanating from the association of dinuclear transition metal tetracarboxylates are important for designing molecular electronic devices. In this study, its influence on both direct and indirect metal–metal interactions, and the electronic structure, in particular transport properties, is discussed.