Construction of 1D and 2D Copper(I) Coordination Polymers Assembled by PhS(CH2)nSPh (n = 1,2) Dithioether Ligands: Surprising Effect of the Spacer Length on the Dimensionality, Cluster Nuclearity and the Fluorescence Properties of the Metal-Organic Framework

International audienceTreatment of CuI with PhSCH2SPh in MeCN solution affords, by a self‐assembly reaction, the monodimensional metal–organic coordination polymer [Cu4I4{μ‐PhS2CH2SPh}2]n (1), in which Cu4(μ3‐I)4 cluster units are linked by the dithioether ligand in a 1D necklace structure. In contrast, the reaction of PhSCH2CH2SPh with CuI results in the formation of the metallopolymer [(CuI)2{μ‐PhS(CH2)2SPh}2]n (2). The 2D network of 2 is built from dimeric Cu2I2 units which are connected by 1,2‐bis(phenylthio)ethane bridging ligands. The solid‐state luminescence spectrum of 1 exhibits a strong emission around 532 nm, whereas a weak emission centred at 413 nm is observed in the case of 2