The Molecular Nature of Redox-Conductive Metal-Organic Frameworks.

ConspectusRedox-conductive metal-organic frameworks (RC-MOFs) are a class of porous materials that exhibit electrical conductivity through a chain of self-exchange reactions between molecularly defined, neighboring redox-active units of differing oxidation states. To maintain electroneutrality, this electron hopping transport is coupled to the translocation of charge balancing counterions. Owing to the molecular nature of the redox active components, RC-MOFs have received increasing attention for potential applications in energy storage, electrocatalysis, reconfigurable electronics, etc. While our understanding of fundamental aspects that govern electron hopping transport in RC-MOFs has improved during the past decade, certain fundamental aspects such as questions that arise from the coupling between electron hopping and diffusion migration of charge balancing counterions are still not fully understood.In this Account, we summarize and discuss our group's efforts to answer some of these fundamental questions while also demonstrating the applicability of RC-MOFs in energy-related applications. First, we introduce general design strategies for RC-MOFs, fundamentals that govern their charge transport properties, and experimental diagnostics that allow for their identification. Selected examples with redox-active organic linkers or metallo-linkers are discussed to demonstrate how the molecular characteristics of the redox-active units inside RC-MOFs are retained. Second, we summarize experimental techniques that can be used to characterize charge transport properties in a RC-MOF. The apparent electron diffusion coefficient,