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.

Palladium nanoparticles stabilized by lightly cross-linked phosphine-decorated polymer immobilized ionic liquids (PIIL) and their PEGylated counterparts (PEGPIIL) are highly effective catalysts for the aqueous phase hydrogenation and sodium borohydride-based reduction of a wide range of nitroaromatic and heteroaromatic compounds under mild conditions with low catalyst loadings. Introduction of extensive cross-linking with tris(4-vinylphenyl)phosphine to isolate the phosphine-based heteroatom and limit the number of surface Pd⋯P interactions did not have a significant influence on catalyst performance. Comparative testing revealed PdNPs immobilized on lightly cross-linked phsophine-decoarted PEGylated polymer to be a highly efficient catalyst for the aqueous phase reduction of nitroarenes with a TON of 36 000 (TOF = 2580 h⁻¹) for hydrogenation and a TON of 274 000 (TOF = 17 125 h⁻¹) for transfer hydrogenation. Even though these reactions occur under diffusion control due the poor solubility of the substrate these values are the highest to be reported for the room temperature aqueous phase reduction of nitroarenes catalyzed by a nanoparticle-based system. A continuous flow reduction of nitrobenzene in a packed bed reactor operated over a period of 250 min with no sign of catalyst deactivation and the corresponding space-time-yield of 0.738 g L⁻¹ min⁻¹ is a marked improvement on that of 0.384 g L⁻¹ min⁻¹ obtained in batch. The same system also catalyzes a tandem Suzuki–Miyaura cross coupling-nitroarene reduction sequence to afford high yields of biaryl amine in an operationally straightforward single-pot procedure. This is a highly versatile protocol which will enable the aromatic nitro fragment to be introduced as a nitro-substituted aryl or heteroaryl halide and as such will lend itself to rapid diversification for the synthesis of a wide range of amines.

Impregnation of phosphine-decorated styrene-based polymer immobilized ionic liquid (PPh₂-PIIL) with ruthenium(III) trichloride resulted in facile reduction of the ruthenium to afford Ru(II)-impregnated phosphine oxide-decorated PIIL (OPPh₂PIIL). The derived phosphine oxide-decorated polymer immobilized ionic liquid-stabilized RuNPs (RuNP@OPPh₂-PIILS) catalyse the highly efficient and selective aqueous phase reduction of the carbonyl group in aryl and heteroaryl ketones and aldehydes, including furfural, as well as the hydrogenation of levulinic acid and its ethyl ester to afford γ-valerolactone (GVL). While this is the first report of RuNPs stabilized by a phosphine oxide-modified support, there appear to be several recent examples of similar serendipitous oxidations during the synthesis of RuNPs by impregnation of a phosphine-decorated polymer with ruthenium trichloride; as these were either misinterpreted or not recognised as such we have carried out a detailed characterization and evaluation of this system. Reassuringly, RuNP@OPPh₂-PIILS generated from phosphine oxide-decorated polymer immobilized ionic liquid (OPPh₂-PIIL) impregnated with ruthenium trichloride is as efficient as that prepared directly from RuCl₃ and PPh₂-PIIL. Incorporation of PEG into the polymer support improved catalyst performance and the initial TOF of 2350 h⁻¹ obtained for the aqueous phase hydrogenation of acetophenone is among the highest to be reported for a ruthenium nanoparticle-based catalyst. Under optimum conditions, RuNP@OPPh₂-PEGPIILS recycled ten times with only a minor reduction in activity and no detectable change in selectivity. High yields and excellent selectivities were also obtained for hydrogenation of the CO across a range of substituted aryl and heteroaryl ketones. Complete hydrogenation of the aromatic ring and CO could also be achieved by increasing the pressure and temperature accordingly. The same system also catalyzes the aqueous phase hydrogenation of furfural under mild conditions with an initial TOF of 3160 h⁻¹ as well as the selective hydrogenation of levulinic acid and its ethyl ester to γ-valerolactone (GVL); reaction times for the latter could be reduced quite significantly by addition of either butyric acid or Amberlyst H-15.

Copper catalysed vicarious nucleophilic substitution of 2-halogeno BODIPYs with alkyl amines, anilines and an amide produces the corresponding 3-aminoBODIPY derivatives.