Construction of two novel 2D layer Mo(W)/Cu/S polymers using bidentate thiolato ligands as linkers

Reactions of thiomolybdate or thiotungstate [MOS3]2− (M = Mo, W) with 3 equiv. of CuS2P(OMe)2 led to the formation of two novel Mo(W)/Cu/S polymers [Et4N][MOS3Cu3{S2P(OMe)2}2] (1, M = Mo; 2, M = W). Single-crystal X-ray diffraction studies reveal that 1 and 2 are the first examples that containing anionic 2D (6,3) net with nest-shaped [MOS3Cu3 · S2P(OMe)2] clusters as 3-connecting nodes and tridentate [S2P(OMe)2]− ligands as linkers. Both 1 and 2 crystallize in a noncentrosymmetric space group and the former polymer shows good second-order NLO performance.