Sequence-Independent Activation of Photocyloadditions Using Two Colors of Light

We exploit two reactive chromophores to establish sequence-independent photochemical activation, employing ortho-methyl benzaldehyde (oMBA) and N,N-(dimethylamino)pyrene aryl tetrazole (APAT) with N-(2-hydroxy)ethyl maleimide (NHEM), without any additives. Critically, the order of...

Photo-initiated oxidation of C–H bonds by diimine complexes of vanadium(v)

The photochemical activation of carbon–hydrogen bonds by vanadium(v)–dioxo and vanadium(v)–oxo–peroxo diimine complexes is described.

Corrole photochemistry

The rapid expansion of photoredox catalysis and artificial photosynthesis has garnered renewed interest in the field of photochemistry. While porphyrins have been widely utilized for a variety of photochemical applications, corrole photochemistry remains underexplored, despite an exponential growth in corrole chemistry. Indeed, less than 4% of all corrole-related publications have studied the photochemistry of these molecules. Since corroles exhibit chemical properties that are distinct from porphyrins and related macrocycles, it is likely that this divergence would also be observed in their photochemical properties. This review provides a comprehensive summary of the extant corrole photochemistry literature. Corroles primarily serve as photosensitizers that transfer energy or an electron to molecular oxygen to form singlet oxygen or superoxide, respectively. While both of these reactive oxygen species can be used to drive chemical reactions, they can also be exploited for photodynamic therapy to treat cancer and other diseases. Although direct photochemical activation of metal–ligand bonds has been less explored, corroles mediate a variety of transformations, particularly oxygen atom transfer reactions. Together, these examples illustrate the diversity of corrole photochemistry and suggest that there are many additional applications yet to be discovered.

Nanocluster-Based Ultralow-Temperature Driven Oxide Gate Dielectrics for High-Performance Organic Electronic Devices

The development of novel dielectric materials with reliable dielectric properties and low-temperature processibility is crucial to manufacturing flexible and high-performance organic thin-film transistors (OTFTs) for next-generation roll-to-roll organic electronics. Here, we investigate the solution-based fabrication of high-k aluminum oxide (Al2O3) thin films for high-performance OTFTs. Nanocluster-based Al2O3 films fabricated by highly energetic photochemical activation, which allows low-temperature processing, are compared to the conventional nitrate-based Al2O3 films. A wide array of spectroscopic and surface analyses show that ultralow-temperature photochemical activation (<60 °C) induces the decomposition of chemical impurities and causes the densification of the metal-oxide film, resulting in a highly dense high-k Al2O3 dielectric layer from Al-13 nanocluster-based solutions. The fabricated nanocluster-based Al2O3 films exhibit a low leakage current density (<10−7 A/cm2) at 2 MV/cm and high dielectric breakdown strength (>6 MV/cm). Using this dielectric layer, precisely aligned microrod-shaped 2,7-dioctyl[1]benzothieno [3,2-b][1] benzothiophene (C8-BTBT) single-crystal OTFTs were fabricated via solvent vapor annealing and photochemical patterning of the sacrificial layer.

Dawn of a new era in industrial photochemistry: the scale-up of micro- and mesostructured photoreactors

Photochemical activation routes are gaining the attention of the scientific community since they can offer an alternative to the traditional chemical industry that mainly utilizes thermochemical activation of molecules. Photoreactions are fast and selective, which would potentially reduce the downstream costs significantly if the process is optimized properly. With the transition towards green chemistry, the traditional batch photoreactor operation is becoming abundant in this field. Process intensification efforts led to micro- and mesostructured flow photoreactors. In this work, we are reviewing structured photoreactors by elaborating on the bottleneck of this field: the development of an efficient scale-up strategy. In line with this, micro- and mesostructured bench-scale photoreactors were evaluated based on a new benchmark called photochemical space time yield (mol·day−1·kW−1), which takes into account the energy efficiency of the photoreactors. It was manifested that along with the selection of the photoreactor dimensions and an appropriate light source, optimization of the process conditions, such as the residence time and the concentration of the photoactive molecule is also crucial for an efficient photoreactor operation. In this paper, we are aiming to give a comprehensive understanding for scale-up strategies by benchmarking selected photoreactors and by discussing transport phenomena in several other photoreactors.