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Novel Metal-Organic Frameworks Incorporating [Cp°2Mo2P4S] (Cp° = 1-tBu-3,4-Me2C5H2), P4S3 and Cu2I2 Building Blocks



The synthesis and characterization of [Cp°2Mo2P4S] (1) and [Cp°2Mo2P2S3] (2) (Cp° = 1-tBu-3,4-Me2C5H2) has been described. The reaction of 1 in CH2Cl2 with 2 equiv. of CuI in MeCN under diffusion conditions gave [(Cp°2Mo2P4S)3(CuI)4]n (6a). The crystal structure of 6a consists of helical substructures of opposed chirality which are formed by the coordination of two Cu2I2 rings to three phosphorus atoms of the cyclo-P4S middle deck of 1. The resulting helix is connected with four helices of the same chirality by front-backside P coordination of another 1 unit. Compound 6a can reversibly include or release CH2Cl2 molecules without loosing its crystalline character. Thus, storing crystals of 6a under CH2Cl2 results in the formation of 6a·0.55CH2Cl2 (6b), the unit cell volume increasing by 113.6 Å3 per formula unit, while in high vacuum the unit cell volume of 6b decreases to the value of 6a. The reaction of 1 with CuI in the presence of P4S3 gave a mixture of two isomeric polymers 7 and 8 of composition [(Cp°2Mo2P4S)(P4S3)(CuI)2]n. The crystal structures of both compounds 7 and 8 contain linear strands of [1(CuI)2]n and [(P4S3)(CuI)2]n with planar Cu2I2 rings as common interface. A two-dimensional framework is formed by interpenetration of both types of strands. The analogous reaction of the mixture of [Cp*2Mo2P4S] (Cp* = C5Me5) and P4S3 with CuI gave [(Cp*2Mo2P4S)(P4S3)(CuI)2]n (9). Contrary to the structures of 7 and 8 in this compound coordination of adjacent P atoms of the η3-P3 ligand and the η2-PS dumbbell leads to the formation of one-dimensional ribbons.