No abstract

The hydrogen bond represents a fundamental interaction widely existing in nature, which plays a key role in chemical, physical and biochemical processes. However, hydrogen bond dynamics at the molecular level are extremely difficult to directly investigate. Here, in this work we address direct electrical measurements of hydrogen bond dynamics at the single-molecule and single-event level on the basis of the platform of molecular nanocircuits, where a quadrupolar hydrogen bonding system is covalently incorporated into graphene point contacts to build stable supramolecule-assembled single-molecule junctions. The dynamics of individual hydrogen bonds in different solvents at different temperatures are studied in combination with density functional theory. Both experimental and theoretical results consistently show a multimodal distribution, stemming from the stochastic rearrangement of the hydrogen bond structure mainly through intermolecular proton transfer and lactam–lactim tautomerism. This work demonstrates an approach of probing hydrogen bond dynamics with single-bond resolution, making an important contribution to broad fields beyond supramolecular chemistry.

The dynamic process of a nucleophilic addition reaction has been investigated in graphene-molecule single-molecule junctions.

Molecular self-assembly into crystallised films or wires on surfaces produces a big family of motifs exhibiting unique optoelectronic properties. However, little attention has been paid to the fundamental mechanism of molecular crystallisation. Here we report a biomimetic design of phosphonate engineered, amphiphilic organic semiconductors capable of self–assembly, which enables us to use real-time in-situ scanning probe microscopy to monitor the growth trajectories of such organic semiconducting films as they nucleate and crystallise from amorphous solid states. The single-crystal film grows through an evolutionary selection approach in a two-dimensional geometry, with five distinct steps: droplet flattening, film coalescence, spinodal decomposition, Ostwald ripening, and self-reorganised layer growth. These sophisticated processes afford ultralong high-density microwire arrays with high mobilities, thus promoting deep understanding of the mechanism as well as offering important insights into the design and development of functional high-performance organic optoelectronic materials and devices through molecular and crystal engineering.

Single‐molecule detection based on electricity can realize direct, real‐time, and label‐free monitoring of the dynamic processes of either chemical reactions or biological functions at the single‐molecule/single‐event level. This provides a fascinating platform to probe detailed information of chemical and biological reactions, including intermediates/transient states and stochastic processes that are usually hidden in ensemble‐averaged experiments, which is of crucial importance to chemical, biological, and medical sciences. Here, the focus is on a valuable survey of the state‐of‐art progress in single‐molecule dynamics studies that are based on electrical nanocircuits formed from one‐dimensional nanoarchitectures and molecular‐tunneling junctions. Further interesting applications, useful statistical‐analysis methods, and future promising directions toward the study of chemical‐reaction dynamics and biomolecular activities are also discussed.

The mechanisms of chemical reactions, including the transformation pathways of the electronic and geometric structures of molecules, are crucial for comprehending the essence and developing new chemistry. However, it is extremely difficult to realize at the single-molecule level. Here, we report a single-molecule approach capable of electrically probing stochastic fluctuations under equilibrium conditions and elucidating time trajectories of single species in non-equilibrated systems. Through molecular engineering, a single molecular wire containing a functional center of 9-phenyl-9-fluorenol was covalently wired into nanogapped graphene electrodes to form stable single-molecule junctions. Both experimental and theoretical studies consistently demonstrate and interpret the direct measurement of the formation dynamics of individual carbocation intermediates with a strong solvent dependence in a nucleophilic-substitution reaction. We also show the kinetic process of competitive transitions between acetate and bromide species, which is inevitable through a carbocation intermediate, confirming the classical mechanism. This unique method creates plenty of opportunities for carrying out single-molecule dynamics or biophysics investigations in broad fields beyond reaction chemistry through molecular design and engineering.

A heterostructure photovoltaic diode featuring an all-solid-state TiO2/graphene/dye ternary interface with high-efficiency photogenerated charge separation/transport is described here. Light absorption is accomplished by dye molecules deposited on the outside surface of graphene as photoreceptors to produce photoexcited electron-hole pairs. Unlike conventional photovoltaic conversion, in this heterostructure both photoexcited electrons and holes tunnel along the same direction into graphene, but only electrons display efficient ballistic transport toward the TiO2 transport layer, thus leading to effective photon-to-electricity conversion. On the basis of this ipsilateral selective electron tunnelling (ISET) mechanism, a model monolayer photovoltaic device (PVD) possessing a TiO2/graphene/acridine orange ternary interface showed ∼86.8% interfacial separation/collection efficiency, which guaranteed an ultrahigh absorbed photon-to-current efficiency (APCE, ∼80%). Such an ISET-based PVD may become a fundamental device architecture for photovoltaic solar cells, photoelectric detectors, and other novel optoelectronic applications with obvious advantages, such as high efficiency, easy fabrication, scalability, and universal availability of cost-effective materials.

Photoelectrocatalytic performance of Cu2O foam electrodes for reduction of CO2 to methanol depends largely on exposed Cu2O{111} facets.