This review focuses on molecular ensemble junctions in which the individual molecules of a monolayer each span two electrodes. This geometry favors quantum mechanical tunneling as the dominant mechanism of charge transport, which translates perturbances on the scale of bond lengths into nonlinear electrical responses. The ability to affect these responses at low voltages and with a variety of inputs, such as de/protonation, photon absorption, isomerization, oxidation/reduction, etc., creates the possibility to fabricate molecule-scale electronic devices that augment; extend; and, in some cases, outperform conventional semiconductor-based electronics. Moreover, these molecular devices, in part, fabricate themselves by defining single-nanometer features with atomic precision via self-assembly. Although these junctions share many properties with single-molecule junctions, they also possess unique properties that present a different set of problems and exhibit unique properties. The primary trade-off of ensemble junctions is complexity for functionality; disordered molecular ensembles are significantly more difficult to model, particularly atomistically, but they are static and can be incorporated into integrated circuits. Progress toward useful functionality has accelerated in recent years, concomitant with deeper scientific insight into the mediation of charge transport by ensembles of molecules and experimental platforms that enable empirical studies to control for defects and artifacts. This review separates junctions by the trade-offs, complexity, and sensitivity of their constituents; the bottom electrode to which the ensembles are anchored and the nature of the anchoring chemistry both chemically and with respect to electronic coupling; the molecular layer and the relationship among electronic structure, mechanism of charge transport, and electrical output; and the top electrode that realizes an individual junction by defining its geometry and a second molecule–electrode interface. Due to growing interest in and accessibility of this interdisciplinary field, there is now sufficient variety in each of these parts to be able to treat them separately. When viewed this way, clear structure–function relationships emerge that can serve as design rules for extracting useful functionality.

Three different benzodithiophene derivatives were designed to isolate the effects of bond topology from that of functional groups in quantum interference to examine the role of the quinone functionality separate from cross-conjugation.

Large‐area molecular tunneling junctions comprising self‐assembled monolayers of redox‐active molecules are described that exhibit two‐terminal bias switching. The as‐prepared monolayers undergo partial charge transfer to the underlying metal substrate (Au, Pt, or Ag), which converts their cores from a quinoid to a hydroquinoid form. The resulting rearomatization converts the bond topology from a cross‐conjugated to a linearly conjugated π system. The cross‐conjugated form correlates to the appearance of an interference feature in the transmission spectrum that vanishes for the linearly conjugated form. Owing to the presence of electron‐withdrawing nitrile groups, the reduction potential and the interference feature lie close to the work function and Fermi level of the metallic substrate. We exploited the relationship between conjugation patterns and quantum interference to create nonvolatile memory in proto‐devices using eutectic Ga–In as the top contact.

Despite their ubiquity, self-assembled monolayers (SAMs) of thiols on coinage metals are difficult to study and are still not completely understood, particularly with respect to the nature of thiol-metal bonding. Recent advances in molecular electronics has highlighted this deficiency due to the sensitivity of tunneling charge-transport to the subtle differences in the overall composition of SAMs and the chemistry of their attachment to surfaces. These advances have also challenged assumptions about the spontaneous formation of covalent thiol-metal bonds. This paper describes a series of experiments that correlate changes in the physical properties of SAMs to photoelectron spectroscopy to unambiguously assign binding energies of non-covalent interactions to physisorbed disulfides. These disulfides can be converted to covalent metal-thiolate bonds by exposure to free thiols, leading to the remarkable observation of the total loss and recovery of length-dependent tunneling charge-transport. The identification and assignment of physisorbed disulfides solves a longstanding mystery and reveals new, dynamic properties in SAMs of thiols.