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Nature Communications Jun 2024Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Excited radicals with picosecond lifetimes have been implied by...
Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Excited radicals with picosecond lifetimes have been implied by numerous photoredox studies, and controversy has arisen as to whether they can actually be catalytically active. We provide direct evidence for the elusive pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. A strategy based on two distinct light absorbers, mimicking the natural photosystems I and II, is used to generate excited radicals, unleashing extreme reduction power and activating C(sp)-Cl and C(sp)-F bonds. Our findings provide a long-sought mechanistic understanding for many previous synthetically-oriented works and permit more rational future photoredox reaction development. The newly developed excitation strategy pushes the current limits of reactions based on multi-photon excitation and very short-lived but highly redox active species.
PubMed: 38834625
DOI: 10.1038/s41467-024-49006-5 -
The Journal of Chemical Physics Jun 2024Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work,...
Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work, isomers of C3H4+ were produced upon electron ionization of propyne and allene molecules and interrogated via infrared spectroscopy inside He nanodroplet matrices. It was found that the spectrum of C3H4+ has at least three distinct groups of bands. The relative intensities of the bands depend on the precursor employed and its pickup pressure, which indicates the presence of at least three different isomers. Two isomers were identified as allene and propyne radical cations. The third isomer, which has several new bands in the range of 3100-3200 cm-1, may be the elusive vinylmethylene H2C=CH-CH+ radical cation. The observed bands for the allene and propyne cations are in good agreement with the results of density functional theory calculations. However, there is only moderate agreement between the new bands and the theoretically calculated vinylmethylene spectrum, which indicates more work is necessary to unambiguously assign it.
PubMed: 38832743
DOI: 10.1063/5.0206412 -
RSC Advances May 2024Aliovalent doping in ceria and defect engineering are important aspects in tuning the properties of ceria for advanced technological applications, especially in the...
Aliovalent doping in ceria and defect engineering are important aspects in tuning the properties of ceria for advanced technological applications, especially in the emerging field of electrocatalytic water-splitting for harvesting renewable energy. However, the ambiguity regarding the choice of dopants/co-dopants and ways to deal with the size difference between dopants and lattice hosts remains a long-standing problem. In this study, ceria was aliovalently codoped with Sc and La while keeping the total concentration of dopants constant; the ionic radius of the former is smaller and that of the latter is larger than Ce. Variations in the relative amounts of these dopants helped to modulate the effective ionic radii and match that of the host. A systematic study on the role of these aliovalent dopants in defect evolution in ceria and in modulating the Ce fraction using powder XRD, Rietveld refinement, positron annihilation lifetime spectroscopy, X-ray photoelectron spectroscopy, Eu photoluminescence, and Raman spectroscopy is presented here. The evolved defects and their dependence on subtle factors other than charge compensation are further correlated with their electrocatalytic activity towards oxygen evolution reaction (OER) in alkaline medium. The catalyst with an optimum defect density, maximum Ce fraction at the surface and the least effective ionic radius difference between the dopants and the host demonstrated the best performance towards the OER. This study demonstrates how effective ionic radius modulation in defect-engineered ceria through a judicious choice of codopants can enhance the catalytic property of ceria and provides immensely helpful information for designing ceria-based heterogeneous catalysts with desired functionalities.
PubMed: 38832250
DOI: 10.1039/d4ra03360d -
Chemical Reviews Jun 2024Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the... (Review)
Review
Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the plasmon can decay through different channels, including nonradiative Landau damping for the generation of plasmon-induced energetic carriers, the so-called hot electrons and holes. The energetic carriers can be collected by transferring to a functional material situated next to the plasmonic component in a hybrid configuration to facilitate a range of photochemical processes for energy or chemical conversion. This article centers on the recent advancement in generating and utilizing plasmon-induced hot electrons in a rich variety of hybrid nanostructures. After a brief introduction to the fundamentals of hot-electron generation and decay in plasmonic nanocrystals, we extensively discuss how to collect the hot electrons with various types of functional materials. With a focus on plasmonic nanocrystals made of metals, we also briefly examine those based upon heavily doped semiconductors. Finally, we illustrate how site-selected growth can be leveraged for the rational fabrication of different types of hybrid nanostructures, with an emphasis on the parameters that can be experimentally controlled to tailor the properties for various applications.
PubMed: 38829921
DOI: 10.1021/acs.chemrev.4c00165 -
ChemSusChem Jun 2024The photosynthetic oxygen-evolving center (OEC) is a unique Mn4CaO5-cluster that catalyzes water splitting into electrons, protons, and dioxygen. Precisely structural...
The photosynthetic oxygen-evolving center (OEC) is a unique Mn4CaO5-cluster that catalyzes water splitting into electrons, protons, and dioxygen. Precisely structural and functional mimicking of the OEC is a long-standing challenge and pressingly needed for understanding the structure-function relationship and catalytic mechanism of O-O bond formation. Herein we report two simple and robust artificial Mn3Ce2O5-complexes that display a remarkable structural similarity to the OEC in regarding of the ten-atom core (five metal ions and five oxygen bridges) and the alkyl carboxylate peripheral ligands. This Mn3Ce2O5-cluster can catalyze the water-splitting reaction on the surface of ITO electrode. These results clearly show that cerium can structurally and functionally replace both calcium and manganese in the cluster. Mass spectroscopic measurements demonstrate that the oxide bridges in the cluster are exchangeable and can be rapidly replaced by the isotopic oxygen of H218O in acetonitrile solution, which supports that the oxide bridge(s) may serve as the active site for the formation of O-O bond during the water-splitting reaction. These results would contribute to our understanding of the structure-reactivity relationship of both natural and artificial clusters and shed new light on the development of efficient water-splitting catalysts in artificial photosynthesis.
PubMed: 38829180
DOI: 10.1002/cssc.202401031 -
Photochemistry and Photobiology Jun 2024The field of sun protection is quickly changing and the research article by Douki et al., published in the current issue of Photochemistry and Photobiology, reported...
An important step towards the comprehensive sun protection: Blue-light exposure inhibits DNA repair in reconstituted human skin and a broadband sunscreen avoids this inhibition.
The field of sun protection is quickly changing and the research article by Douki et al., published in the current issue of Photochemistry and Photobiology, reported key experimental data that will certainly help the development of better sun care products. Mutagenic photoproducts (CPDs, cyclobutane pyrimidine dimers and 6-4PPs, pyrimidine-6-4-pyrimidone photoproducts) were formed in the reconstructed human epidermis (RHE) by UVB (312 nm) irradiation, and their concentrations were detected by HPLC-MS/MS as a function of time after the UVB treatment. RHE had been previously exposed or not (control) to blue light (427 nm). Both CPDs and 6-4PPs were shown to last longer in blue-light irradiated RHE, proving the inhibition of the DNA repair by blue light exposure. This is a highly relevant information because sunscreens allow people to enjoy longer periods under the sun and consequently, to endure very high doses of blue light. The work also reported results obtained with RHEs previously treated with a sunscreen formulation containing a broadband filter that offers blue-light protection. Interestingly, authors observed that the DNA repair was not significantly inhibited in RHE previously treated with the sunscreen offering broadband protection. Readers will find a scientifically sound proof of the importance of blue-light protection in sun care products.
PubMed: 38828502
DOI: 10.1111/php.13979 -
Journal of Chemical Theory and... Jun 2024We reconsider recent methods by which direct dynamics calculations of electronically nonadiabatic processes can be carried out while requiring only adiabatic potential... (Review)
Review
We reconsider recent methods by which direct dynamics calculations of electronically nonadiabatic processes can be carried out while requiring only adiabatic potential energies and their gradients. We show that these methods can be understood in terms of a new generalization of the well-known semiclassical Ehrenfest method. This is convenient because it eliminates the need to evaluate electronic wave functions and their matrix elements along the mixed quantum-classical trajectories. The new approximations and procedures enabling this advance are the curvature-driven approximation to the time-derivative coupling, the generalized semiclassical Ehrenfest method, and a new gradient correction scheme called the time-derivative matrix (TDM) scheme. When spin-orbit coupling is present, one can carry out dynamics calculations in the fully adiabatic basis using potential energies and gradients calculated without spin-orbit coupling plus the spin-orbit coupling matrix elements. Even when spin-orbit coupling is neglected, the method is useful because it allows calculations by electronic structure methods for which nonadiabatic coupling vectors are unavailable. In order to place the new considerations in context, the article starts out with a review of background material on trajectory surface hopping, the semiclassical Ehrenfest scheme, and methods for incorporating decoherence. We consider both internal conversion and intersystem crossing. We also review several examples from our group of successful applications of the curvature-driven approximation.
PubMed: 38819014
DOI: 10.1021/acs.jctc.4c00424 -
Angewandte Chemie (International Ed. in... May 2024gem-Diborylalkanes are highly valuable building blocks in organic synthesis and the pharmaceutical chemistry due to their ability to participate in multi-step...
gem-Diborylalkanes are highly valuable building blocks in organic synthesis and the pharmaceutical chemistry due to their ability to participate in multi-step cross-coupling transformations, allowing for the rapid generation of molecular complexity. While progress has been made in their synthetic metholodology, the construction of β-tertiary and C(sp3)-rich gem-diborylalkanes remains a synthetic challenge due to substrate limitations and steric hindrance issues. An approach is presented that utilizes synergistic photoredox and copper catalysis to achieve efficient C(sp3)-C(sp3) cross-coupling of alkyl N-hydroxyphthalimide esters, which can be easily obtained from alkyl carboxylic acids, with diborylmethyl species, providing a series of C(sp3)-rich gem-diborylalkanes with 1°, 2°, and even 3° β positions. Furthermore, this approach can also be applied to complex medicinal compounds and natural products, offering rapid access to molecular complexity and late-stage functionalization of C(sp3)-rich drug candidates. Mechanistic experiments revealed that diborylmethyl Cu(I) species participated in both the photoredox process and the key C(sp3)-C(sp3) bond-forming step.
PubMed: 38818649
DOI: 10.1002/anie.202401782 -
Science (New York, N.Y.) May 2024Layered metal-halide perovskites, or two-dimensional perovskites, can be synthesized in solution, and their optical and electronic properties can be tuned by changing...
Layered metal-halide perovskites, or two-dimensional perovskites, can be synthesized in solution, and their optical and electronic properties can be tuned by changing their composition. We report a molecular templating method that restricted crystal growth along all crystallographic directions except for [110] and promoted one-dimensional growth. Our approach is widely applicable to synthesize a range of high-quality layered perovskite nanowires with large aspect ratios and tunable organic-inorganic chemical compositions. These nanowires form exceptionally well-defined and flexible cavities that exhibited a wide range of unusual optical properties beyond those of conventional perovskite nanowires. We observed anisotropic emission polarization, low-loss waveguiding (below 3 decibels per millimeter), and efficient low-threshold light amplification (below 20 microjoules per square centimeter).
PubMed: 38815024
DOI: 10.1126/science.adl0920 -
The Journal of Physical Chemistry... Jun 2024We combined ring-polymer molecular dynamics (MD) and ab initio MD with nonadiabatic MD to study the effects of nuclear quantum effects (NQEs) on interlayer electron...
We combined ring-polymer molecular dynamics (MD) and ab initio MD with nonadiabatic MD to study the effects of nuclear quantum effects (NQEs) on interlayer electron transfer and electron-hole recombination at the g-CN/TiO interface. Our simulations indicate that NQEs significantly affect electron transfer and electron-hole recombination dynamics, accelerating both processes. NQEs deform the g-CN layer and expedite the movement of carbon and nitrogen atoms, thus, enhancing charge delocalization and interlayer coupling. This improved overlap between electronic state wave functions enhances nonadiabatic couplings, facilitating electron transfer and recombination. In addition to the enhanced nonadiabatic couplings accelerating electron transfer, the presence of NQEs narrows the energy gap and delays decoherence by mitigating overall fluctuations, because of restricted TiO movements overwhelming enhanced g-CN fluctuations, thereby making the recombination faster. This work provides valuable insights into NQEs in light-element systems and contributes to guiding the development of highly efficient photocatalysts.
PubMed: 38814291
DOI: 10.1021/acs.jpclett.4c01329