Assembly of Coordination Polymers Using Thioether-Functionalized Octasilsesquioxanes: Occurrence of (CuX)(n) Clusters (X=Br and I) within 3D-POSS Networks

For the first time, POSS-based coordination polymers (CPs) have been structurally characterized. These CPs were obtained in high yield via self-assembly reactions of thioether-functionalized polysilsesquioxanes with Cu-I salts under mild conditions. Single crystal analyses revealed the formation of 3D networks incorporating different secondary building units (SBUs) as connection nodes. The nature of the -SAr functionality allows a fine-tuning of the cluster nuclearity, that is, butterfly-shaped Cu2X2 or closed cubane-type Cu4I4 cores. As such, the resulting hybrid materials exhibit a combination of high thermal stability arising from the inorganic POSS core along with interesting luminescent properties conferred by the cubane cluster core. Furthermore, the occurrence of channels has been shown crystallographically in the case of the Cu4I4 cluster containing CP.