Novel Metal‐Organic Frameworks Incorporating [Cp° 2 Mo 2 P 4 S] (Cp° = 1‐ t Bu‐3,4‐Me 2 C 5 H 2 ), P 4 S 3 and Cu 2 I 2 Building Blocks

The synthesis and characterization of [Cp° 2 Mo 2 P 4 S] ( 1 ) and [Cp° 2 Mo 2 P 2 S 3 ] ( 2 ) (Cp° = 1‐ t Bu‐3,4‐Me 2 C 5 H 2 ) has been described. The reaction of 1 in CH 2 Cl 2 with 2 equiv. of CuI in MeCN under diffusion conditions gave [(Cp° 2 Mo 2 P 4 S) 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 Cu 2 I 2 rings to three phosphorus atoms of the cyclo ‐P 4 S 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 CH 2 Cl 2 molecules without loosing its crystalline character. Thus, storing crystals of 6a under CH 2 Cl 2 results in the formation of 6a· 0.55CH 2 Cl 2 ( 6b ), the unit cell volume increasing by 113.6 Å 3 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 P 4 S 3 gave a mixture of two isomeric polymers 7 and 8 of composition [(Cp° 2 Mo 2 P 4 S)(P 4 S 3 )(CuI) 2 ] n . The crystal structures of both compounds 7 and 8 contain linear strands of [ 1 (CuI) 2 ] n and [(P 4 S 3 )(CuI) 2 ] n with planar Cu 2 I 2 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* 2 Mo 2 P 4 S] (Cp* = C 5 Me 5 ) and P 4 S 3 with CuI gave [(Cp* 2 Mo 2 P 4 S)(P 4 S 3 )(CuI) 2 ] n ( 9 ). Contrary to the structures of 7 and 8 in this compound coordination of adjacent P atoms of the η 3 ‐P 3 ligand and the η 2 ‐PS dumbbell leads to the formation of one‐dimensional ribbons.