Solid-state synthesis, crystal structure, and nonlinear refractive and absorptive properties of the new cluster (n-Bu4N)2[MoOS3Cu3BrCl2]

Abstract

The title compound (n-Bu4N)2[MoOS3Cu3BrCl2] was synthesized for nonlinear optical studies by reaction of (NH4)2MoO2S2, CuCl, and (n-Bu)N4Br in the solid state. Single-crystal X-ray analysis reveals that the cluster anion assumes a nest-shaped structure. The crystal has a monoclinic symmetry with a space group of P21/c. Cell parameters are a = 21 779(5) Å, b = 11.169(7) Å, c = 22.012(3) Å, β = 118.61(1)°, V = 4700.7 Å3, and Z = 4. The crystal structure was refined to R = 0.056, Rw = 0.058. The cluster exhibits interesting self-defocusing and nonlinear absorptive properties. These nonlinear optical properties of the cluster and the electronic spectrum, XPS, and oxidation-reduction behavior of the cluster are discussed.