A fundamental aim in the field of catalysis is the development of new modes of small molecule activation. One approach toward the catalytic activation of organic molecules that has received much attention recently is visible light photoredox catalysis. In a general sense, this approach relies on the ability of metal complexes and organic dyes to engage in single-electron-transfer (SET) processes with organic substrates upon photoexcitation with visible light.

Many of the most commonly employed visible light photocatalysts are polypyridyl complexes of ruthenium and iridium, and are typified by the complex tris(2,2′-bipyridine) ruthenium(II), or Ru(bpy)32+ (Figure 1). These complexes absorb light in the visible region of the electromagnetic spectrum to give stable, long-lived photoexcited states.1,2 The lifetime of the excited species is sufficiently long (1100 ns for Ru(bpy)32+) that it may engage in bimolecular electron-transfer reactions in competition with deactivation pathways.3 Although these species are poor single-electron oxidants and reductants in the ground state, excitation of an electron affords excited states that are very potent single-electron-transfer reagents. Importantly, the conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes.






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Figure 1


Ruthenium polypyridyl complexes: versatile visible light photocatalysts.

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Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

Many, if not most, redox reactions are coupled to proton transfers. This includes most common sources of chemical potential energy, from the bioenergetic processes that power cells to the fossil fuel combustion that powers cars. These proton-coupled electron transfer or PCET processes may involve multiple electrons and multiple protons, as in the 4 e–, 4 H+ reduction of dioxygen (O2) to water (eq 1), or can involve one electron and one proton such as the formation of tyrosyl radicals from tyrosine residues (TyrOH) in enzymatic catalytic cycles (eq 2). In addition, many multi-electron, multi-proton processes proceed in one-electron and one-proton steps. Organic reactions that proceed in one-electron steps involve radical intermediates, which play critical roles in a wide range of chemical, biological, and industrial processes. This broad and diverse class of PCET reactions are central to a great many chemical and biochemical processes, from biological catalysis and energy transduction, to bulk industrial chemical processes, to new approaches to solar energy conversion. PCET is therefore of broad and increasing interest, as illustrated by this issue and a number of other recent reviews.

/pdf/thermochemistry-of-proton-coupled-electron-transfer-reagents-v04esq6den.pdf

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications

New physics occurs in semiconductors when one or more dimensions of the crystal are reduced to a size comparable to bulk electron delocalization lengths (tens to hundreds of angstroms). The properties of "quantum dots" or semiconductor nanocrystals are now being studied, as techniques to fabricate the crystallites are developed. Temperature-dependent electron diffraction studies on nanocrystals of CdS show a large depression in the melting temperature with decreasing size, as a larger fraction of the total number of atoms is on the surface. Thermal stability may play a role in determining the uses of semiconductor nanocrystals.

https://science.sciencemag.org/content/sci/256/5062/1425.full.pdf

Melting in semiconductor nanocrystals.

This is a review and analysis of the optical properties of quantum crystallites, with principal emphasis on the electro-optic Stark effect and all optical third order nonlinearity. There are also introductory discussions on physical size regimes, crystallite synthesis, quantum confinement theory, and linear optical properties. The experiments describe CdSe crystallites, exhibiting strong confinement of electrons and holes, and CuCl crystallites, exhibiting weak confinement of the exciton center of mass. In the CdSe system, neither the Stark effect nor the third order nonlinearity is well understood. The Stark shifts appear to be smaller than calculated, and field inducted broadening also occurs. The third order nonlinearity is only modestly stronger than in bulk material, despite theoretical prediction. Unexpectedly large homogeneous widths, due to surface carrier trapping, in the nominally discrete crystallite excited states appear to be involved. The CuCl system shows far narrower spectroscopic homogeneous widths, and corresponds more closely to an ideal quantum dot in the weak confinement limit. CuCl also exhibits exciton superradiance at low temperature. Surface chemistry and crystallite encapsulation are critical in achieving the predicted large Stark and third order optical effects in II-VI and III-V crystallites.

Quantum crystallites and nonlinear optics

A substantial amount of work has been carried out in the area of nanocomposite materials for optical applications. Composites are typically constructed by embedding an optically functional phase into a processable, transparent matrix material. By doing so, the optical properties can be utilized in more technologically important forms such as films and fibers. This review covers many areas of optical composite research to date. Composites with second- and third-order nonlinearities and laser amplification properties are discussed with examples from the recent literature. Other composites, including transparent magnets, may be made using similar structures. The principles used to construct these composites may have important technological applications soon and are therefore summarized in this review.

Nanocomposite Materials for Optical Applications

External magnetic field and magnetic isotope effects on the dynamic behavior of radical pairs in solutions have been studied theoretically, where the relaxation of their electron spins was taken into account. The decay observed with some radical pairs in micellar solutions under high magnetic fields is successfully interpreted in terms of the relaxation mechanism, and the magnetic field dependence of the relaxation rates is calculated for a model system.

Theoretical study of relaxation mechanism in magnetic field effects on chemical reactions.

Effets du champ magnetique sur les reactions photochimiques de la naphtoquinone-1,4 en micelle de SDS etudies par photolyse laser (ns). Vitesses de declin des radicaux naphitosemiquinones reduites par un champ magnetique externe de 0,03 T. Mecanisme de relaxation

Hisaharu Hayashi

Papers

Theoretical study of relaxation mechanism in magnetic field effects on chemical reactions.

Laser-photolysis study of the photochemical reactions of naphthoquinones in a sodium dodecyl sulfate micelle under high magnetic fields

The external magnetic field effect on the singlet sensitized photolysis of dibenzoyl peroxide

Laser-photolysis study of the external magnetic field effect upon the photochemical processes of carbonyl compounds in micelles

CIDEP study of the photochemical reactions of carbonyl compounds showing the external magnetic field effect in a micelle