Synthesis and nonlinear optical absorptive and refractive properties of several novel nest-shaped clusters, and crystal structures of [MoI(bPy)2][MoOS3Cu3I2(bPy)] and [MoOS 3Cu 3I(Phen) 2

Abstract

Nest-shaped clusters [MI(bPy) 2][MOS 3Cu 3I 2(bPy)] (M=Mo, 1; M=W, 2) were synthesized by the treatment of (NH 4) 2MO 2S 2, CuI and Et 4NI with 2,2′-bipyridyl (bPy) in CH 3CN. Both clusters show a very interesting structure, and consist of two parts: a nest-shaped structural unit [MOS 3Cu 3I 2(bPy)] − and complex ion [MI(bPy) 2] +. By the reaction of [Et 4N] 4[Mo 2O 2S 6Cu 6I 6] with Phen (1,10-phenanthroline), or bPy, or bMe-bPy (4,4′-dimethyl-2,2′-bipyridyl), we prepared nest-shaped clusters [MoOS 3Cu 3IR 2] (R=Phen, 3; R=bPy, 4; R=bMe-bPy, 5). The crystal structures of [MoI(bPy) 2][MoOS 3Cu 3I 2(bPy)] ( 1) and [MoOS 3Cu 3I(Phen) 2] ( 3) were characterized by X-ray diffraction. Their nonlinear optical (NLO) properties were studied with a 7-ns pulsed laser at 532 nm. Cluster 1 has large NLO absorption and NLO refraction, its α 2 and n 2 values were calculated as 3.0×10 −10 m W −1 and −3.0×10 −17 m 2 W −1 in a 3.4×10 −5 mol dm −3 DMF solution, respectively. Cluster 2 only exhibits very strong NLO absorptive property, its α 2 value is 1.0×10 −9 m W −1 when measured in a 4.8×10 −5 mol dm −3 DMF solution. Clusters 4 and 5 have strong NLO absorption too. Their α 2 values were calculated as 7×10 −11 m W −1 and 3.5×10 −10 m W −1, respectively. Cluster 3 only shows moderate NLO absorption, its α 2 value is ∼10 −11 m W −1.