MOFs and COFs in Electronics: Bridging the Gap between Intrinsic Properties and Measured Performance

Abstract Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) hold promise for advanced electronics due to their tunable structural and electronic properties. However, discrepancies in reported electrical conductivities underscore the critical role of measurement methodologies. This review explores how intrinsic charge transport mechanisms (band‐like vs hopping) and extrinsic factors (grain boundaries, contact resistance) influence performance. This review critically examines the impact of common characterization methods – including two‐probe, four‐probe, van‐der‐Pauw, thin‐film, pellet, and single‐crystal techniques – on the assessment of electronic properties in MOFs and COFs. Case studies on copper benzenehexathiol (Cu 3 BHT) and copper hexahydroxytriphenylene (Cu 3 (HHTP) 2 ) illustrate how factors such as grain boundaries and contact resistance strongly affect measured conductivities. Advanced microscopic and spectroscopic techniques (conductive atomic force microscopy, terahertz spectroscopy) provide nanoscale or dynamic insights but may not reflect macroscopic device behavior. The necessity of standardized, method‐specific reporting and careful selection of characterization strategies to bridge the gap between intrinsic material properties and real‐world electronic performance are highlighted.