Abstract: Metal and covalent organic frameworks (MOFs and COFs) are distinct families of fundamentally molecule-based materials with permanent porosity. These systems exhibit record undoped conductivities up to ~103 S/cm, and are of growing interest for applications including electrocatalysis and chemical sensing. However, inherent experimental challenges have obfuscated their systematic electrical characterization, limiting progress. Indeed, bulk sample properties are strongly influenced by their preparation method, which dictate the crystal polymorph, number and type of defects, grain boundaries, and residual impurities. We are pursuing an alternative, “bottom-up,” approach to develop robust structure-property relationships in these materials by evaluating the conductance of framework-relevant structures in atomically-precise single-molecule junctions. We will present our investigations of charge transport across different linkage groups used in framework construction, as well as across relevant three-dimensional nodes comprising C, Si, and Os.

We will also outline strategies for the preparation of multicomponent self-assembled monolayers (SAMs). Such systems may be of interest, for example, to modulate the reactivity of surface-bound homogeneous catalysts by controlling their secondary coordination sphere. Our initial attempts to utilize redox-active metal bis(terpyridine) complexes as modular SAM building blocks has revealed important complications resulting from ligand dissociation and/or counterion loss, providing key insights that serve to guide subsequent directions.