Direct measurement of the radiative lifetime of the A2Σ+(υ′ = 0, K′ = 1, J′ = 32) state of OH and OD

The radiative lifetime of the A²Σ⁺(υ′ = 0, K′ = 1, J′ = 3/2) state of OH and OD has been directly measured by following the decay of fluorescence excited by light from a frequency doubled dye laser. Stern-Volmer extrapolation of the results to zero pressure gave τ(OH) = 788 ± 13 ns and τ(OD) = 754 ± 12 ns.     

Directly visualizing carrier transport and recombination at individual defects within 2D semiconductors

Two-dimensional semiconductors (2DSCs) are promising materials for a wide range of optoelectronic applications. While the fabrication of 2DSCs with thicknesses down to the monolayer limit has been demonstrated through a variety of routes, a robust understanding of carrier transport within these materials is needed to guide the rational design of improved practical devices. In particular, the influence of different types of structural defects on transport is critical, but difficult to interrogate experimentally. Here, a new approach to visualizing carrier transport within 2DSCs, Carrier Generation-Tip Collection Scanning Electrochemical Cell Microscopy (CG-TC SECCM), is described which is capable of providing information at the single-defect level. In this approach, carriers are locally generated within a material using a focused light source and detected as they drive photoelectrochemical reactions at a spatially-offset electrolyte interface created through contact with a pipet-based probe, allowing carrier transport across well-defined, µm-scale paths within a material to be directly interrogated. The efficacy of this approach is demonstrated through studies of minority carrier transport within mechanically-exfoliated n-type WSe₂ nanosheets. CG-TC SECCM imaging experiments carried out within pristine basal planes revealed highly anisotropic hole transport, with in-plane and out-of-plane hole diffusion lengths of 2.8 µm and 5.8 nm, respectively. Experiments were also carried out to probe recombination across individual step edge defects within n-WSe₂ which suggest a significant surface charge (∼5 mC m⁻²) exists at these defects, significantly influencing carrier transport. Together, these studies demonstrate a powerful new approach to visualizing carrier transport and recombination within 2DSCs, down to the single-defect level.

Probe-based electrochemical techniques can be used to map carrier transport and recombination within two-dimensional semiconductors.     

Diverse Reactivity of Dienes with Pentaphenylborole and 1-Phenyl-2,3,4,5-Tetramethylborole Dimer

The reactions of a monomeric borole and a dimeric borole with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were investigated. The monomeric borole reacted at ambient temperature whereas heat was required to crack the dimer to form the monomer and induce reactivity. 2,3-Dimethyl-1,3-butadiene reacts to give diverse products resulting from a cycloaddition process with the B−C moiety of the boroles acting as a dienophile, followed by rearrangements to furnish bicyclic species. For 1,3-cyclohexadiene, a [4+2] process is observed in which 1,3-cyclohexadiene serves as the dienophile and the boroles as the diene partner. The experimental results are corroborated with mechanistic theoretical calculations that indicate boroles can serve as either a diene or dienophile in cycloaddition reactions with dienes.     

Strategies Towards Capturing Nitrogenase Substrates and Intermediates via Controlled Alteration of Electron Fluxes

Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N₂ to NH₄⁺, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N₂ and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions.