Metal-organic materials afford access to synthetic tunability and rational property design unmatched by traditional inorganic solid-state materials. While this tunability has been utilized with great success to generate metal-organic frameworks with applications in gas storage, gas separations, and chemical sensing, achievement of long-range electronic communication in metal-organic frameworks represents a comparatively open research frontier. One method of engendering long-range electronic communication in metal-organic frameworks is to utilize not only paramagnetic metal ions, but also paramagnetic organic linkers in framework construction. To this end, design, synthesis, and characterization of organic radical-based metal-organic frameworks will be discussed. A new semiquinoid radical-based metal-organic framework that exhibits high electronic conductivity, ferrimagnetic ordering, and cation insertion mediated by organic mixed-valence will be shown. Post-synthetic chemical redox control over this metal-organic framework will be demonstrated, with subsequent changes in framework conductivity and magnetic ordering shown. Overall, the transition metal-semiquinoid system will be established as a particularly promising scaffold for achieving tunable long-range electronic communication in metal-organic frameworks.

Electronic conductivity, ferrimagnetic ordering, and reductive insertion in semiquinoid metal-organic frameworks

251st National Meeting (2016)

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