Electrochemical host–guest interactions in a disordered oligosilyl coordination polymer†‡

We synthesize and study the charge transfer properties of a oligosilyl coordination polymer formed from zirconium clusters. Although the product lacks long range order, spectroscopic and computational evidence suggest that the metal–ligand bond is formed, and the principle crystallographic reflections closely match those simulated from inter-node spacings matching that of the ligand. The porous polymer allows for the incorporation of guest molecules as demonstrated by the intercalation of 7,7,8,8-tetracyanoquinodimethane (TCNQ). Charge transfer is predicted from DFT and experimentally observed by infrared spectroscopy, solid-state ²⁹Si nuclear magnetic spectroscopy, and voltammetry.