Helically chiral N,N,O,O‐boron chelated dipyrromethenes showed solution‐phase circularly polarized luminescence (CPL) in the red region of the visible spectrum (λ em(max) from 621 to 663 nm). The parent dipyrromethene is desymmetrised through O chelation of boron by the 3,5‐ortho‐phenolic substituents, inducing a helical chirality in the fluorophore. The combination of high luminescence dissymmetry factors (|g lum| up to 4.7 ×10−3) and fluorescence quantum yields (Φ F up to 0.73) gave exceptionally efficient circularly polarized red emission from these simple small organic fluorophores, enabling future application in CPL‐based bioimaging.

Gold(I)-triflimide (AuNTf 2 )complexes of H-KITPHOS and o-MeO-KITPHOS have been prepared and shown to be efficient catalysts for a range of intramolecular cyclisations to afford phenols, acylindenes, alkylidene oxazoles, tetrahydropyrans and lactones, in the majority of cases these catalysts are superior to those previously reported.

Structural data derived from X-ray powder diffraction and EXAFS spectroscopy are presented for iodosyl benzene (PhlO) and the imido analogue, PhlNS02-4-Me-C6H4, which indicate that these compounds are polymeric in the solid state.

Gold nanoparticles stabilized by phosphine-decorated polymer immobilized ionic liquids (AuNP@PPh2-PIILP) is an extremely efficient multiproduct selective catalyst for the sodium borohydride-mediated reduction of nitrobenzene giving N-phenylhydroxylamine, azoxybenzene, or aniline as the sole product under mild conditions and a very low catalyst loading. The use of a single nanoparticle-based catalyst for the partial and complete reduction of nitroarenes to afford three different products with exceptionally high selectivities is unprecedented. Under optimum conditions, thermodynamically unfavorable N-phenylhydroxylamine can be obtained as the sole product in near quantitative yield in water, whereas a change in reaction solvent to ethanol results in a dramatic switch in selectivity to afford azoxybenzene. The key to obtaining such a high selectivity for N-phenylhydroxylamine is the use of a nitrogen atmosphere at room temperature as reactions conducted under an inert atmosphere occur via the direct pathway and are essentially irreversible, while reactions in air afford significant amounts of azoxy-based products by virtue of competing condensation due to reversible formation of N-phenylhydroxylamine. Ultimately, aniline can also be obtained quantitatively and selectively by adjusting the reaction temperature and time accordingly. Introduction of PEG onto the polyionic liquid resulted in a dramatic improvement in catalyst efficiency such that N-phenylhydroxylamine could be obtained with a turnover number (TON) of 100 000 (turnover frequency (TOF) of 73 000 h–1, with >99% selectivity), azoxybenzene with a TON of 55 000 (TOF of 37 000 h–1 with 100% selectivity), and aniline with a TON of 500 000 (TOF of 62 500 h–1, with 100% selectivity). As the combination of ionic liquid and phosphine is required to achieve high activity and selectivity, further studies are currently underway to explore whether interfacial electronic effects influence adsorption and thereby selectivity and whether channeling of the substrate by the electrostatic potential around the AuNPs is responsible for the high activity. This is the first report of a AuNP-based system that can selectively reduce nitroarenes to either of two synthetically important intermediates as well as aniline and, in this regard, is an exciting discovery that will form the basis to develop a continuous flow process enabling facile scale-up.

Reactions of bicyclic α‐P4S3I2 with Hpthiq gave solutions containing α‐P4S3(pthiq)I and α‐P4S3(pthiq)2, where Hpthiq is the conformationally constrained chiral secondary amine 1‐phenyl‐1,2,3,4‐tetrahydroisoquinoline. The expected diastereomers have been characterised by complete analysis of their 31P{1H} NMR spectra. Hindered P–N bond rotation in the amide iodide α‐P4S3(pthiq)I caused greater broadening of peaks in the room‐temperature spectrum of one diastereomer than in that of the other. At 183 K, spectra of two P–N bond rotamers for each diastereomer were observed and analysed. The minor rotamers showed strong evidence for steric crowding, having large diastereomeric differences in 1J(P–P) and 2J(P–S–P) couplings (49 Hz, 16 % of value, and 4.4 Hz, 19 % of value, respectively).