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Hierarchically Ordered Two-Dimensional Coordination Polymers Assembled from Redox-Active Dimolybdenum Clusters.
Journal of the American Chemical Society 2018 August 30
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 Mo2 (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 Å) 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 E1/2 = -1.275 V versus ferrocene/ferrocenium that can be ascribed to the [Mo2 (INA)4 ]0/-1 redox couple, with an associated standard heterogeneous electron transfer rate constant ks = 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.
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