Enantioselective catalysis of excited-state photoreactions remains a substantial challenge in synthetic chemistry, and intermolecular photoreactions have proven especially difficult to conduct in a stereocontrolled fashion. Herein, we report a highly enantioselective intermolecular [2 + 2] cycloaddition of 3-alkoxyquinolones catalyzed by a chiral hydrogen-bonding iridium photosensitizer. Enantioselectivities as high as 99% ee were measured in reactions with a range of maleimides and other electron-deficient alkene reaction partners. An array of kinetic, spectroscopic, and computational studies supports a mechanism in which the photocatalyst and quinolone form a hydrogen-bonded complex to control selectivity, yet upon photoexcitation of this complex, energy transfer sensitization of maleimide is preferred. The sensitized maleimide then reacts with the hydrogen-bonded quinolone–photocatalyst complex to afford a highly enantioenriched cycloadduct. This finding contradicts a long-standing tenet of enantioselective photochemistry that held that stereoselective photoreactions require strong preassociation to the sensitized substrate in order to overcome the short lifetimes of electronically excited organic molecules. This system therefore suggests that a broader range of alternate design strategies for asymmetric photocatalysis might be possible.

An accurate description of a subcycle pulsed beam (SCPB) is presented based on the complex-source model. The fields are exact solutions of Maxwell's equations and applicable to a focused pulsed beam with a pulse duration down to and below one cycle of the carrier wave and with arbitrary polarization state. Depending on the pulse duration, the pulse is blueshifted, and its wings are chirped. This effect, which we refer to as "self-induced blueshift" goes beyond the carrier-envelope description. The corresponding phase is a temporal analog of the Gouy phase. The energy gain of a relativistic electron swept over by an SCPB is very sensitive to the proper form chosen to describe the pulse.

A novel flat-response x-ray detector has been developed for the measurement of radiation flux from a hohlraum. In order to obtain a flat response in the photon energy range of 0.1-4 keV, it is found that both the cathode and the filter of the detector can be made of gold. A further improvement on the compound filter can then largely relax the requirement of the calibration x-ray beam. The calibration of the detector, which is carried out on Beijing Synchrotron Radiation Facility at Institute of High Energy Physics, shows that the detector has a desired flat response in the photon energy range of 0.1-4 keV, with a response flatness smaller than 13%. The detector has been successfully applied in the hohlraum experiment on Shenguang-III prototype laser facility. The radiation temperatures inferred from the detector agree well with those from the diagnostic instrument Dante installed at the same azimuth angle from the hohlraum axis, demonstrating the feasibility of the detector.

The long-lived triplet excited states of transition metal photocatalysts can activate organic substrates via either energy-or electron-transfer pathways, and the rates of these processes can be influenced by rational tuning of the reaction conditions. The characteristic reactive intermediates that are generated by each of these activation modalities, however, are distinct and can exhibit very different reactivity patterns. Herein, we show that the photocatalytic reactions of benzoylformate esters with alkenes can be directed towards either Paternò-Büchi cycloadditions under conditions that favor energy transfer or allylic functionalization reactions under superficially similar conditions that favor electron transfer. These studies provide a framework for designing other divergent photocatalytic methods that produce different sets of reaction outcomes under photoredox and triplet sensitization conditions.

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Nonlinear optical processes are governed by the relative-phase relationships among the relevant electromagnetic fields in these processes. In this Report, we describe the physics of arbitrary manipulation of Raman-resonant four-wave-mixing process by artificial control of relative phases. As a typical example, we show freely designable optical-frequency conversions to extreme spectral regions, mid-infrared and vacuum-ultraviolet, with near-unity quantum efficiencies. Furthermore, we show that such optical-frequency conversions can be realized by using a surprisingly simple technology where transparent plates are placed in a nonlinear optical medium and their positions and thicknesses are adjusted precisely. In a numerical simulation assuming practically applicable parameters in detail, we demonstrate a single-frequency tunable laser that covers the whole vacuum-ultraviolet spectral range of 120 to 200 nm.