Metal- and covalent-organic frameworks (MOFs and COFs) are distinct families of fundamentally molecular materials with permanent porosity. Extensive studies over the past five years have yielded new MOF and COF materials that claim impressive undoped conductivities up to ~10<sup>3</sup> S/cm and 10<sup>-5</sup>, respectively. Such systems are of growing interest for applications including electrocatalysis and electrochemical energy storage. However, inherent experimental challenges have obfuscated their systematic electrical characterization. For example, bulk electrical measurements are strongly influenced by framework preparation methods, as these dictate the crystal polymorph, number and type of defects (different redox states; missing struts or nodes), grain boundaries, and residual impurities. We are interested in how scanning tunneling microscope-based break junction (STM-BJ) studies of “framework fragments”, model molecules with framework-inspired structures, may provide insights into the intrinsic electronic properties of their analogous bulk systems. We present initial STM-BJ investigations of transport across different linkage groups used in the construction of COFs, and find these groups are also capable of binding to gold.

Charge transport through single-molecule framework fragments

ACS Spring Meeting 2021

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