The ability to tune the properties of metal–organic frameworks via careful selection of metal and ligand offers the potential for rational design not found in traditional inorganic materials. While this tunability has been utilized extensively for applications in gas storage, separations, and catalysis, control over the charge transport properties of these materials has not been as thoroughly explored. One strategy for developing metal–organic materials displaying long-range electronic interactions is the use of a continuous pathway of paramagnetic metal ions bridged by paramagnetic organic ligands. Radical-based semiquinoid frameworks have been established as a promising class of electronic materials, but the ability to tune the electronic properties of these frameworks via substitution of the metal ion has not yet been investigated. The synthesis and characterization of early transition metal semiquinoid frameworks will be discussed. These materials show significantly different electronic structures from the isostructural iron phases, as evidenced by changes in the electronic conductivity and magnetic properties. Ongoing work to probe the mechanism of charge transport and the electrochemical reactivity of these materials will be highlighted. Overall, these results demonstrate the ability to tune the electronic structure of metal–organic materials and provide insights into the design of new conductive materials.

Control over electronic delocalization and conductivity in mixed-valence semiquinoid frameworks

253rd National Meeting (2017)

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