Synthesis, crystal structure and nonlinear optical properties of two novellinear cluster polymers {[MoOS3Cu3(CN)(py)(3)]center dot 0.5C(6)H(6)}(n) and [WOS3Cu3(CN)(py)(4)](n)

Cluster polymers {[MoOS3Cu3(CN)(py)(3)]. 0.5C(6)H(6)}(n) 1 and [WOS3Cu3(CN) (py)(4)](n) 2 were synthesized by the reaction of (NH4)(2)MO2S2 (M = Mo, W) and CuCN with py. Their structures have been characterized by X-ray diffra ction. Both of them show neutral nest-shaped structural units, and every st ructural unit forms two Cu1-N1-C1-Cu3 bridges with two other structural uni ts leading to infinite one-dimensional polymers. In every unit cell of {[Mo OS3Cu3(CN)(py)(3)]. 0.5C(6)H(6)}(n) there are four [MoOS3Cu3(CN)(py)(3)] st ructural units and two benzene molecules, and the four structural units are from four independent linear polymer molecules which are parallel. In ever y unit cell of polymer 2, there are four [WOS3Cu3(CN)(py)(4)] structural un its too, but they are only from two parallel linear polymer molecules. Poly mer 1 shows good nonlinear optical (NLO) absorptive and NLO refractive prop erties, whereas strong NLO properties of polymer 2 are not observed.