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

With aromatic and aliphatic thiol-S donor Schiff base ligands, the copper-sulfur clusters, [(L1)CuCu](ClO)·DMF·0.5CHOH () and [(L2)CuCu(μ-S)(μ-O)](ClO)·4HO, respectively, have been reported ( 2017, 53, 3334); HL1/HL2 are 2-(((3-methylthiophen-2-yl)methylene)amino)benzene/ethanethiol). Complex comprises a wheel shaped CuS framework, made up of interlinked Cu{μ-S(R)} units. To understand the properties with relevance to the Cu site and to check whether self-assembly generates similar type clusters to , three complexes, [(L3)CuCu](ClO)·(CH)O·2.5HO (), [(L3)CuCu](ClO)·1.25(CH)O·1.25CHOH·2HO (), and [(L3)CuCu](ClO)·2(CH)O·HO () have been synthesized with supporting ligands HL3 (HL3 = 2-((furan-2-ylmethylene)amino)benzenethiol when X = -H; X = -Cl or -CF to thiol-S are HL3 and HL3 ligands, respectively). The X-ray structures of and feature a similar CuS architecture to . The spectroscopic properties and the X-ray structures revealed that - are fully spin delocalized mixed valence (MV) of type clusters. The structural parameters of the NCu{μ-S(R)} units of and closely resemble those of the MV binuclear Cu 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 Cu site.