Chiral multiresonant thermally activated delayed fluorescence (MR-TADF) materials show great potential as emitters in circularly polarized (CP) organic light-emitting diodes (CP-OLEDs) owing to their bright and narrowband CP emission. Here, two new chiral MR-TADF emitters tBuPh-BN and DPA-tBuPh-BN possessing intrinsically helical chirality have been synthesized and studied. The large steric interactions between the tert-butylphenyl groups not only induce the helical chirality but also provide a notable configurational stability to the enantiomers. Racemic mixtures of tBuPh-BN and DPA-tBuPh-BN show narrowband emission at 490 and 477 nm with full-width at half maximum (FWHM) of 25 and 28 nm and photoluminescence quantum yields, Φ_PL, of 85 and 54% in toluene. The separated enantiomers of tBuPh-BN and DPA-tBuPh-BN show symmetric circularly polarized luminescence (CPL) with respective dissymmetry factors |g_PL| values of 1.5 × 10⁻³ and 0.9 × 10⁻³. The hyperfluorescence organic light-emitting diodes (HF-OLEDs) with tBuPh-BN and DPA-tBuPh-BN acting as terminal emitters and 2,3,4,5,6-penta-(9H-carbazol-9-yl)benzonitrile (5CzBN) as their assistant dopant exhibited, respectively, maximum external quantum efficiencies (EQE_max) of 20.9 and 15.9% at 492 and 480 nm with FWHM of 34 and 38 nm. This work demonstrates a strategy for developing intrinsically helically chiral MR-TADF emitters possessing significant configurational stability, which can be used in HF-OLEDs.

A general and highly enantioselective method for the preparation of tetra‐substituted 3‐hydroxyphthalide esters via isothiourea‐catalysed acylative dynamic kinetic resolution (DKR) is reported. Using (2S,3R)‐HyperBTM (5 mol %) as the catalyst, the scope and limitations of this methodology have been extensively probed, with high enantioselectivity and good to excellent yields observed (>40 examples, up to 99 %, 99 : 1 er). Substitution of the aromatic core within the 3‐hydroxyphthalide skeleton, as well as aliphatic and aromatic substitution at C(3), is readily tolerated. A diverse range of anhydrides, including those from bioactive and pharmaceutically relevant acids, can also be used. The high enantioselectivity observed in this DKR process has been probed computationally, with a key substrate heteroatom donor O⋅⋅⋅acyl‐isothiouronium interaction identified through DFT analysis as necessary for enantiodiscrimination.

New approaches to achieve facile and reversible dihydrogen activation are of importance for synthesis, catalysis, and hydrogen storage. Here we show that low-coordinate magnesium oxide complexes [{(^RDipnacnac)Mg}₂(μ-O)] 1, with ^RDipnacnac = HC(RCNDip)₂, Dip = 2,6-iPr₂C₆H₃, R = Me (1a), Et (1b), iPr (1c), readily react with dihydrogen under mild conditions to afford mixed hydride-hydroxide complexes [{(^RDipnacnac)Mg}₂(μ-H)(μ-OH)] 4. Dehydrogenation of complexes 4 is strongly dependent on remote ligand substitution and can be achieved by simple vacuum-degassing of 4c (R = iPr) to regain 1c. Donor addition to complexes 4 also releases hydrogen and affords donor adducts of magnesium oxide complexes. Computational studies suggest that the hydrogen activation mechanism involves nucleophilic attack of an oxide lone pair at a weakly bound H₂···Mg complex in an S_N2-like manner that induces a heterolytic dihydrogen cleavage to yield an MgOH and an MgH unit. Alternative synthetic routes into complex 4b from a magnesium hydride complex have been investigated and the ability of complexes 1 or 4 to act as catalysts for the hydrogenation of 1,1-diphenylethene (DPE) has been tested.

The development of methods to allow the selective acylative dynamic kinetic resolution (DKR) of tetra‐substituted lactols is a recognised synthetic challenge. In this manuscript, a highly enantioselective isothiourea‐catalysed acylative DKR of tetra‐substituted morpholinone and benzoxazinone‐derived lactols is reported. The scope and limitations of this methodology have been developed, with high enantioselectivity and good to excellent yields (up to 89 %, 99 : 1 er) observed across a broad range of substrate derivatives incorporating substitution at N(4) and C(2), di‐ and spirocyclic substitution at C(5) and C(6), as well as benzannulation (>35 examples in total). The DKR process is amenable to scale‐up on a 1 g laboratory scale. The factors leading to high selectivity in this DKR process have been probed through computation, with an N−C=O⋅⋅⋅isothiouronium interaction identified as key to producing ester products in highly enantioenriched form.

Environmentally acceptable and renewably sourced flame retardants are in demand. Recent studies have shown that the incorporation of the biopolymer lignin into a polymer can improve its ability to form a char layer upon heating to a high temperature. Char layer formation is a central component of flame-retardant activity. The covalent modification of lignin is an established technique that is being applied to the development of potential flame retardants. In this study, four novel modified lignins were prepared, and their char-forming abilities were assessed using thermogravimetric analysis. The lignin was obtained from date palm wood using a butanosolv pretreatment. The removal of the majority of the ester groups from this heavily acylated lignin was achieved via alkaline hydrolysis. The subsequent modification of the lignin involved the incorporation of an azide functional group and copper-catalysed azide–alkyne cycloaddition reactions. These reactions enabled novel organophosphorus heterocycles to be linked to the lignin. Our preliminary results suggest that the modified lignins had improved char-forming activity compared to the controls. ³¹P and HSQC NMR and small-molecule X-ray crystallography were used to analyse the prepared compounds and lignins.

The development of synthetic methods for the catalytic enantioselective preparation of planar chiral paracyclophane derivatives is of considerable interest to the synthetic community. To date, relatively few successful and effective organocatalytic approaches to this molecular class have been reported. This manuscript describes effective isothiourea catalysed acylative kinetic (KR) and dynamic kinetic resolution (DKR) approaches to the generation of a range of planar chiral paracyclophane macrocycles with excellent levels of enantioselectivity. Effective KR of configurationally stable planar chiral paracyclophanols with 12‐ and 13‐membered ansa ‐chains is demonstrated (6 examples, s = up to 50) using 5 mol% of the isothiourea ( R )‐BTM and isobutyric anhydride. Application to configurationally labile macrocyclic phenols with 14 to 18‐membered ansa ‐chains allows their effective acylative DKR, generating the desired products with excellent enantioselectivity (25 examples, up to 95% yield and 98:2 er).