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Near-UV excitation of non-heme Fe IV [double bond, length as m-dash]O complexes results in light intensity dependent increase in reaction rates for the oxidation of C-H bonds even at low temperature (-30 °C). The enhancement of activity is ascribed to the ligand-to-[Fe IV [double bond, length as m-dash]O] charge transfer character of the near-UV bands to generate a highly reactive [(L + ) Fe III -O*] species. The enhancement is not observed with visible/NIR excitation of the d-d absorption bands.

The formation and spectroscopic characterization of a superoxido cobalt(iii) and a peroxido dicobalt(iii) species formed in the temperature dependent reversible reaction of a cobalt(ii) precursor with O 2 is described. The electronic nature of each species is explored in their reactivity with organic substrates.

A delicate interplay of anisotropic hydrophobic/hydrophilic, π-π stacking, ionic and hydrogen bond interactions determine the strength of hydrogelators and are considered key factors in efforts to design potent small molecule hydrogelators. Here we show that solvent deuteration and electrolytic strength affect the strength of hydrogels formed from amino acid modified C 3 -symmetric cyclohexane trisamides profoundly. Gels formed by self-assembly through heating/cooling of solutions or by pH switching show up to a 30 °C increase in their melting temperatures in D 2 O compared to H 2 O. The unusually large solvent isotope effect on gel formation and thermal properties indicates that, in contrast to expectations, hydrogen bonding is not the primary determinant of gel strength but instead that hydrophobic interactions between the gelator molecules and the terminal carboxylic acid units are of greater importance. A conclusion that is supported by a similarly large effect of electrolytes on gel strength.

The contrasting early-time photodynamics of two related Ru/Pt photocatalysts with very different photocatalytic H2 generation capabilities are reported. Ultrafast equilibration (535 ± 17 fs) creates an electron reservoir on the peripheral ligands of the ester substituted complex, allowing a dramatic increase in photocatalytic performance. This insight opens the way towards a novel design strategy for H2 generating molecular photocatalysts.

A high yield synthetic route for the preparation of N6 coordinated heteroleptic Ir(III) complexes using bidentate polypyridyl type ligands is described. The complexes are near-blue emitters and show microsecond emission lifetimes, high emission quantum yields and have two quasi-reversible reduction processes between -1.0 and -1.3 V vs. Ag/AgCl.

The spectroscopic characterisation of the (μ-1,2-peroxido)diiron(iii) species formed transiently upon reaction of [Fe(ii)(NN)3](2+) complexes with H2O2 by UV/vis absorption and resonance Raman spectroscopy is reported. The intermediacy of such species in the disproportionation of H2O2 is demonstrated.

The isolation and definitive assignment of the species formed upon electrochemical oxidation of nitro-spiropyran (SP) is reported. The oxidative aryl C-C coupling at the indoline moiety of the radical cation to form covalent dimers of the ring-closed form is demonstrated. The coupling is blocked with a methyl substituent para to the indoline nitrogen.

First principle simulations of an extended hexameric molecular switch are reported. The full switching of the system is explained by investigating the nature of the excited states of all possible isomers. A new multi-addressable asymmetric structure is proposed.

A dispersion of graphene in ethanol was achieved using solvent exchange from N-methyl-2-pyrrolidone (NMP) that enables broader application of dispersed graphene.

High turnover enantioselective alkene cis-dihydroxylation is achieved with H(2)O(2) catalysed by manganese based complexes containing chiral carboxylato ligands.

Covalent attachment of the enzymes glucose oxidase and catalase to carbon nanotubes enables the tandem catalytic conversion of glucose and H(2)O(2) formed to power autonomous movement of the nanotubes.

Molecular memory devices based on dithienylethene switch modified ITO electrodes undergo reversible ring opening/closing both photo- and electro-chemically with non-destructive electrochemical readout.

A molecular approach to the powering of multi-component nano-devices capable of autonomous translational and rotational motion through the conversion of chemical to kinetic energy is reported.

Catalytic alkane oxidation with high selectivity using peracids and an (N4Py)Fe complex is presented and the role of [(N4Py)Fe(IV)=O]2+ species, molecular oxygen and hydroxyl radicals in the catalysis is discussed.