Bis(μ-thiolato)-dicopper Containing Fully Spin Delocalized Mixed Valence Copper-Sulfur Clusters and Their Electronic Structural Properties with Relevance to the CuA Site.

Abstract

With aromatic and aliphatic thiol-S donor Schiff base ligands, the copper-sulfur clusters, [(L1)8CuI6CuII2](ClO4)2·DMF·0.5CH3OH (1) and [(L2)12CuI5CuII11(μ4-S)(μ4-O)6](ClO4)·4H2O, respectively, have been reported ( Chem. Commun. 2017, 53, 3334); HL1/HL2 are 2-(((3-methylthiophen-2-yl)methylene)amino)benzene/ethanethiol). Complex 1 comprises a wheel shaped Cu8S8 framework, made up of interlinked Cu2{μ-S(R)}2 units. To understand the properties with relevance to the CuA site and to check whether self-assembly generates similar type clusters to 1, three complexes, [(L3)8CuI6CuII2](ClO4)2·(C2H5)2O·2.5H2O (2), [(L3Cl)8CuI6CuII2](ClO4)2·1.25(C2H5)2O·1.25CH3OH·2H2O (3), and [(L3CF3)8CuI6CuII2](ClO4)2·2(C2H5)2O·H2O (4) have been synthesized with supporting ligands HL3X (HL3 = 2-((furan-2-ylmethylene)amino)benzenethiol when X = -H; X = -Cl or -CF3 para to thiol-S are HL3Cl and HL3CF3 ligands, respectively). The X-ray structures of 3 and 4 feature a similar Cu8S8 architecture to 1. The spectroscopic properties and the X-ray structures revealed that 2-4 are fully spin delocalized mixed valence (MV) of class-III type clusters. The structural parameters of the N2Cu2{μ-S(R)}2 units of 3 and 4 closely resemble those of the MV binuclear CuA site. With the aid of UV-vis-NIR, EPR, and spectroelectrochemical studies, the electronic properties of these complexes have been described in comparison with the MV model complexes and CuA site.