Hierarchically Ordered Two-Dimensional Coordination Polymers Assembled from Redox-Active Dimolybdenum Clusters

Coordination polymers (CPs) supporting tunable through-framework conduction and responsive properties are of significant interest for enabling a new generation of active devices. However, such architectures are rare. We report a redox-active CP composed of two-dimensional (2D) lattices of coordinatively bonded Mo-2(INA)(4) clusters (INA = isonicotinate). The 2D lattices are commensurately stacked and their ordering topology can be synthetically tuned. The material has a hierarchical pore structure (pore sizes distributed between 7 and 33 angstrom) and exhibits unique CO2 adsorption (nominally Type VI) for an isotherm collected at 195 K. Furthermore, cyclic voltammetry and electrokinetic analyses identify a quasi-reversible feature at E-1/2 = -1.275 V versus ferrocene/ferrocenium that can be ascribed to the [Mo-2(INA)(4)](0/-1) redox couple, with an associated standard heterogeneous electron transfer rate constant k(s) = 1.49 s(-1). The tunable structure, porosity, and redox activity of our material may render it a promising platform for CPs with responsive properties.