Conductive Metal-Organic Frameworks

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TECHNICAL SUMMARY:With the support of the Solid State and Materials Chemistry program in the Division of Materials Research, new synthetic strategies will be developed in pursuit of metal-organic frameworks that exhibit facile ionic and/or electronic charge mobility. The synthetic tunability of metal-organic frameworks is expected to stimulate inquiry into new physical phenomena such as nanometer scale pore confinement effects and framework-centered charge distribution on ion mobility as well as, electron correlation in one-dimensional materials, and the electronic and magnetic properties of low dimensional systems. Such investigations are of immediate interest for their potential battery applications as electrode or solid electrolyte component materials, electrocatalysis, thermoelectric devices and ultra-capacitors. Porous materials with high ion mobility can be prepared by engendering frameworks with delocalized or otherwise inaccessible charges in order to yield uncoordinated and pore-confined single-ion conductors. This will include the preparation of materials containing ionic metal clusters, ionic organic linkers, inclusion of bulky counterions, and characterizing ion mobility trends with respect to ion identity, pore dimensions, pore topography, framework topology, and crystallite morphology. Leveraging the modular nature of metal-organic frameworks in order to include reversible redox couples in both the inorganic and organic components of the material will target new electronically conductive frameworks. Other synthetic strategies not yet developed in this class of materials will also be explored. This will include optimization of electron correlation along one-dimensional chains of metal centers, the inclusion of stable organic radical, and tuning the band structure via ligand functionalization and inclusion of adventitious guest species. Doing so will allow investigation of charge mobility in porous structures from the perspective of fundamental coordination chemistry, a technique commonly reserved only for molecular species. NON-TECHNICAL SUMMARY:Metal-organic frameworks are a new class of solid materials with porous network structures the surfaces of which can be chemically modified to suit a wide range of potential applications, notably gas storage, chemical separations, and catalysis. By adapting these materials to be electrically conductive through the movement of ions and electrons, new phenomena will be explored that are of fundamental interest in chemistry, energy storage, and condensed matter physics. This work will expand the understanding of how to control the formation of new materials and manipulate the electronic and ionic charge transport properties therein. With the support of the Solid State and Materials Chemistry program in the Division of Materials Research, new porous materials will be created of potential interest as component materials in advanced batteries, electrocatalysis, thermoelectric devices, and ultra-capacitors. In doing so, this work will broadly impact these key technologies, resulting in a legacy of new synthetic techniques and a fundamental understanding of conductive materials, while additionally contributing to the education and training of undergraduate, graduate, and postdoctoral students in the synthesis and characterization of new materials. As a related endeavor, the principle investigator will continue to lead an effort in the Department of Chemistry at UC Berkeley to found a materials chemistry major.