Long-range charge transport (LRCT) in molecular wires is crucial for the advancement of molecular electronics but remains insufficiently understood due to complex transport mechanisms and their dependencies on molecular structure. While short-range charge transport is typically dominated by off-resonant tunneling, which decays exponentially with molecular length, recent studies have highlighted certain molecular structures that facilitate LRCT with minimal attenuation over several nanometers. This Perspective reviews the latest progress in understanding LRCT, focusing on chemical designs and mechanisms that enable this phenomenon. Key strategies include π-conjugation, redox-active centers, and stabilization of radical intermediates, which support LRCT through mechanisms such as coherent resonant tunneling or incoherent hopping. We discuss how the effects of molecular structure, length, and temperature influence charge transport, and highlight emerging techniques like the Seebeck effect for distinguishing between transport mechanisms. By clarifying the principles behind LRCT and outlining future challenges, this work aims to guide the design of molecular systems capable of sustaining efficient long-distance charge transport, thereby paving the way for practical applications in molecular electronics and beyond.
https://pubs.acs.org/doi/10.1021/jacs.4c11431