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Topology has emerged as a field for describing and controlling order and matter, and thereby the physical properties of materials. There are several largely disparate fields focused on examining and manipulating topology. One of these arenas is in the realm of real space, manipulating systems in terms of their spatial properties, to control the corresponding structural, mechanical, and self- assembling responses. Much of the work in soft matter topology falls within this domain. A second arena is in the domain of momentum or k-space wherein topology controls the features of the electronic band structure of materials, and topologically non-trivial features result in the development of materials with truly unique properties. This work focuses squarely on the realm of condensed matter physics. Here, we review concepts of real- and k-space topology and propose areas for convergence between these two disparate fields. 

Molecular orbital symmetry plays a pivotal role in determining chemical reaction mechanisms. The process of changing chemical reactants into products must transition along a pathway that conserves molecular orbital symmetry to ensure continuity. This principle is so fundamental that reactions that do not conserve symmetry are typically considered “forbidden” due to the high resultant energy barriers. Here, it is demonstrated that it is possible to electrically catalyze these forbidden transitions when a single molecule is bound between two electrodes in a nanoscale junction. A cycloaddition reaction is induced in a norbornadiene (NBD) derivative, converting it to quadricyclane (QC) by utilizing nanoconfinement to place the molecule into a configuration that is far from equilibrium and applying a small voltage to the molecular junction. Traditionally, this reaction can only be induced photochemically due to orbital symmetry selection rules. By directly tracking the reaction dynamics in situ using single‐molecule Raman spectroscopy, it is shown that for this reaction to be electrically catalyzed the molecule must be sterically maneuvered into a configuration near the transition state at the peak of the energy barrier prior to applying the voltage needed to successfully induce the forbidden transition is applied. 

Abstract The utilization of single molecule electronic devices represents a significant avenue toward advancing next-generation circuits. Recent investigations have notably augmented our understanding of the optoelectronic characteristics exhibited by diverse single molecule materials. This comprehensive review underscores the latest progressions in probing photo-induced electron transport behaviors within molecular junctions. Encompassing both single molecule and self-assembled monolayer configurations, this review primarily concentrates on unraveling the fundamental mechanisms and guiding principles underlying photo-switchable devices within single molecule junctions. Furthermore, it presents an outlook on the obstacles faced and future prospects within this dynamically evolving domain. 

The molecular electronic devices based on self-assembled monolayer (SAM) on metal surfaces demonstrate novel electronic functions for device minimization yet are unable to realize in practical applications, due to their instability against oxidation of the sulfur-metal bond. This paper describes an alternative to the thiolate anchoring group to form stable SAMs on gold by selenides anchoring group. Because of the formation of strong selenium-gold bonds, these stable SAMs allow us to incorporate them in molecular tunnel junctions to yield extremely stable junctions for over 200 days. A detailed structural characterization supported by spectroscopy and first-principles modeling shows that the oxidation process is much slower with the selenium-gold bond than the sulfur-gold bond, and the selenium-gold bond is strong enough to avoid bond breaking even when it is eventually oxidized. This proof of concept demonstrates that the extraordinarily stable SAMs derived from selenides are useful for long-lived molecular electronic devices and can possibly become important in many air-stable applications involving SAMs. 

Dipyridyl molecular junctions often show intriguing conductance switching behaviors with mechanical modulations, but the mechanisms are still not completely revealed. By applying the ab initio -based adiabatic simulation method, the configuration evolution and electron transport properties of dipyridyl molecular junctions in stretching and compressing processes are systematically investigated. The numerical results reveal that the dipyridyl molecular junctions tend to form specific contact configurations during formation processes. In small electrode gaps, the pyridyls almost vertically adsorb on the second Au layers of the tip electrodes by pushing the top Au atoms aside. These specific contact configurations result in stronger molecule–electrode couplings and larger electronic incident cross-sectional areas, which consequently lead to large breaking forces and high conductance. On further elongating the molecular junctions, the pyridyls shift to the top Au atoms of the tip electrodes. The additional scattering of the top Au atoms dramatically decreases the conductance and switches the molecular junctions to the lower conductive states. Perfect cyclical conductance switches are obtained as observed in the experiments by repeatedly stretching and compressing the molecular junctions. The O atom in the side-group tends to hinder the pyridyl from adsorbing on the second Au layer and further inhibits the conductance switch of the dipyridyl molecular junction.