A New Building Block for Organometallic–Inorganic Hybrid Polymers: The Mixed Group 15/16 Element Ligand Complex [Cp* 2 Mo 2 (μ,η 2:2 ‐PSe) 2 (μ‐Se)] (Cp* = C 5 Me 5 )

The synthesis and spectroscopic characterization of [Cp* 2 Mo 2 P 2 Se 3 ] ( 1 ; Cp* = C 5 Me 5 ) and its use as a molecular building block in the formation of copper(I) halide polymers is described. The reaction of 1 in CH 2 Cl 2 with 2 equiv. of CuBr and CuI in CH 3 CN under diffusion conditions gave [(Cp* 2 Mo 2 P 2 Se 3 ) 2 (CuBr) 2 ] ( 2 ) and [(Cp* 2 Mo 2 P 2 Se 3 )(CuX) 3 (CH 3 CN)] n (X = I; 3 / 4 ), respectively. The structure of 2 is distinguished by a central Cu 2 Br 2 ring coordinated on each side by a tripledecker complex through one of its P atoms. A 2D network is formed by weak interactions between Se atoms of neighboring molecules. Compound [(Cp* 2 Mo 2 P 2 Se 3 )(CuI) 3 (CH 3 CN)] n exists in two isomeric forms 3 and 4 . The crystal structure of 3 can be described as a two‐dimensional polymer that is formed by ribbons containing looped chains of three Cu 2 I 2 rings and attached [Cp* 2 Mo 2 P 2 Se 3 ] molecules. The structure of 4 contains a ribbon in which tripledecker molecules are linked through their P atoms to (CuI) 6 clusters. The ribbons are connected by weak Se ··· Se interactions. The reaction of a mixture of 1 and P 4 Se 3 with CuI gave [(Cp* 2 Mo 2 P 2 Se 3 )(P 4 Se 3 )(CuI) 2 ] n . The crystal structure analysis of 5 reveals a new type of organometallic–inorganic framework in which 1 and P 4 Se 3 are linked by Cu 2 I 2 rings.