Search

Metal-based photosensitizers commonly undergo quantitative intersystem crossing into photoactive triplet excited states. In contrast, organic photosensitizers often feature weak spin-orbit coupling and low intersystem crossing efficiencies, leading to photoactive singlet excited states. By modifying the well-known acridinium dyes, we obtained a new family of organic photocatalysts, the isoacridones, in which both singlet- and triplet-excited states are simultaneously photoactive. These new isoacridone dyes are synthetically readily accessible and show intersystem crossing efficiencies of up to 52%, forming microsecond-lived triplet excited states (T 1 ), storing approximately 1.9 eV of energy. Their photoactive singlet excited states (S 1 ) populated in parallel have only nanosecond lifetimes, but store ∼0.4 eV more energy and act as strong oxidants. Consequently, the new isoacridone dyes are well suited for applications requiring parallel triplet-triplet energy transfer and photoinduced electron transfer elementary steps, which have become increasingly important in modern photocatalysis. In proof-of-principle experiments, the isoacridone dyes were employed for Birch-type arene reductions and C-C couplings via sensitization-initiated electron transfer, substituting the commonly used iridium or ruthenium based photocatalysts. Further, in combination with a pyrene-based annihilator, sensitized triplet-triplet annihilation upconversion was achieved in an all-organic system, where the upconversion quantum yield correlated with the intersystem crossing quantum yield of the photosensitizer. This work seems relevant in the greater contexts of developing new applications that utilize biphotonic photophysical and photochemical behavior within metal-free systems., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The deracemisation of fourfold stereogenic cobalt(III) diketonates with a chiral photocatalyst is described. With only 0.5 mol% menthyl Ru(bpy) 3 2+ photocatalyst, an enantiomeric enrichment of up to 88 : 12 e.r. was obtained for the major meridional diastereomers. Moreover, a distribution of configurationally stable diastereomers distinct from the thermodynamic ratio was observed upon reaching the photostationary state.

The organocatalytic epoxidation of unactivated alkenes using aqueous hydrogen peroxide provides various indispensable products and intermediates in a sustainable manner. While formyl functionalities typically undergo irreversible oxidations when activating an oxidant, an atropisomeric two-axis aldehyde capable of catalytic turnover was identified for high-yielding epoxidations of cyclic and acyclic alkenes. The relative configuration of the stereogenic axes of the catalyst and the resulting proximity of the aldehyde and backbone residues resulted in high catalytic efficiencies. Mechanistic studies support a non-radical alkene oxidation by an aldehyde-derived dioxirane intermediate generated from hydrogen peroxide through the Payne and Criegee intermediates., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Recent developments in preparative photocatalysis have reshaped synthetic strategies and now represent an integral part of current organic chemistry. Due to their favourable electrochemical and photophysical properties, the nowadays most frequently used photocatalysts are based on precious Ru- and Ir-polypyridyl complexes. Apart from that, organic catalysts such as the acridinium salts are now commonly employed to complement transition metals to provide potentially sustainable strategies amenable to large-scale synthesis. In this feature article, the design, synthesis and application of aminoacridinium photoredox catalysts as well as their exceptionally broad range of redox properties are highlighted. Due to their modularity, this burgeoning class of organophotocatalysts is anticipated to contribute significantly to synthetic methodology development and the translation to a wide range of innovative implementations.