Solid State Synthesis, Crystal Structure, Decomposition Reactions, and Optical Nonlinearity of a Twin-Nest-Shaped Cluster Compound, [Et4N]4[Mo2O2S6Cu 6I6]

Abstract

The reaction of (NH4)2[MoO2S2], CuI, and Et4NI in solid state produces a twin-nest-shaped cluster compound [Et4N]4[Mo2O2S6Cu 6I6]. The cluster anion consists of two nest-shaped fragments interconnected through a four-membered Cu(I)2Cu ring. The structure of the cluster has been characterized by X-ray diffraction: monoclinic, space group C2/c, a = 24.680(1) Å, b = 21.328(5) Å, c = 13.638(4) Å, β= 114.51(3)°, V = 6532(4) Å3, Z = 4, R = 0.043, Rw = 0.054. The cluster easily decomposes into two halves when treated with ligands such as py or PPh3. The cluster also exhibits both strong nonlinear optical absorption and optical self-defocusing effect (effective α2 = 4 × 10-10 m W-1, n2 = - 6 × 10-17 m2 W-1, when measured with a 2 × 10-3 M acetonitrile solution).