Solid State Synthesis, Crystal Structure, Decomposition Reactions, and Optical Nonlinearity of a Twin-Nest-Shaped Cluster Compound, [Et₄N]₄[Mo₂O₂S₆Cu₆I₆]

Abstract

The reaction of (NH 4 ) 2 [MoO 2 S 2 ], CuI, and Et 4 NI in solid state produces a twin-nest-shaped cluster compound [Et 4 N] 4 [Mo 2 O 2 S 6 Cu 6 I 6 ]. The cluster anion consists of two nest-shaped fragments interconnected through a four-membered Cu(I) 2 Cu ring. The structure of the cluster has been characterized by X-ray diffraction: monoclinic, space group C 2/ c, a = 24.680(1) Å, b = 21.328(5) Å, c = 13.638(4) Å, β = 114.51(3)°, V = 6532(4) Å 3, Z = 4, R = 0.043, R w = 0.054. The cluster easily decomposes into two halves when treated with ligands such as py or PPh 3 . The cluster also exhibits both strong nonlinear optical absorption and optical self-defocusing effect (effective α 2 = 4 × 10 - 10 m W -1, n 2 = − 6 × 10 - 17 m 2 W -1, when measured with a 2 × 10 - 3 M acetonitrile solution).