Cluster-Containing Coordination Polymers Built Upon (Cu2I2S2)(m) Units (m=2, 3) and ArSCH2Ca parts per thousand CCH2SAr Ligands: Is the Cluster Size Dependent Upon Steric Hindrance or Ligand Rigidity?

Two equivalents of CuI react with p-MeC6H4SCH2Ca parts per thousand CCH2SC6H4-p-Me (L2) to form the 2D network [(Cu4I4)(p-MeC6H4SCH2Ca parts per thousand CCH2SC6H4-p-Me)(2)] (n) (polymer 2) contrasting with the previously reported reaction with C6H5SCH2Ca parts per thousand CCH2SC6H5 (L1) which makes a 3D network [(Cu6I6)(C6H5SCH2Ca parts per thousand CCH2SC6H5)(3)] (n) (polymer 1) (2009, Dalton Trans. 948). The crystal structure of the latter polymer has been re-determined at 115, 155, 195, 235 and 275 K to study the impact of the recording temperature on the metric parameters, notably the Cu center dot center dot center dot Cu distances within the hexagonal prism Cu6I6 cluster. Steric hindrance between a 2D/(Cu4I4) versus 3D/(Cu6I6) appears to drive the selectivity. Upon using the ligand o-MeC6H4SCH2Ca parts per thousand CCH2SC6H4-o-Me (L3) with CuI, a new material (polymer 3) is formed but no X-ray structure determination was possible. From obvious steric considerations and the presence of a high energy emission characteristic of the well-known Cu4I4 cluster (absent in the Cu6I6 one), and the similarity in emission lifetime for both high and low energy emission of polymers 2 and 3, the nature of this polymer was proposed to be [(Cu4I4)(o-MeC6H4SCH2Ca parts per thousand CCH2SC6H4-o-Me)(2)] (n) .