For quaternary ammonium, pyridinium, or imidazolium anion–cationic substituents, a linear relationship can be established between the reactivity of metal Schiff base catalysts and the Hammett constants of their anion–cationic substituents with multi-atomic anions on ligand based on the theoretical and experimental works. Copyright © 2015 John Wiley & Sons, Ltd.

The C−D bond stretching vibrations of deuterated dimethyl sulfoxide ([D₆]DMSO) and the C₂−H bond stretching vibrations of 1,1,1,5,5,5-hexafluoropentane-2,4-dione (hfac) ligand in anion are chosen as probes to elucidate the solvent–solute interaction between chelate-based ionic liquids (ILs) and DMSO by vibrational spectroscopic studies. The indirect effect from the interaction of the adjacent S=O functional group of DMSO with the cation [C₁₀mim]⁺ and anion [Mn(hfac)₃]⁻ of the ILs leads to the blue-shift of the C−D stretching vibrations of DMSO. The C₂−H bond stretching vibrations in hfac ligand is closely related to the ionic hydrogen bond strength between the cation and anion of chelate-based ILs. EPR studies reveal that the crystal field of the central metal is kept when the chelate-based ILs are in different microstructure environment in the solution.

Higher catalytic performances of N,N′,N′′-trihydroxyisocyanuric acid (THICA), N,N-dihydroxypyromellitimide (NDHPI), and N-hydroxynaphthalimide (NHNI) than that of N-hydroxyphthalimide (NHPI) have been demonstrated recently in aerobic oxidation. Herein, the rational design of reactive multi-nitroxyl organocatalysts has been addressed theoretically by using systematic analysis of some important properties and catalytic activities of yet-to-be-synthesized catalysts. Our results show that 1) NHNI and its analogue, similar to THICA, unlike NHPI and others, are unsuitable for solvent- or mediator-free catalysis due to their strong intramolecular hydrogen-bonding interactions; 2) increasing the reactive hydroxyimide groups on the same aromatic ring, or doped N atoms or ionic-pair groups onto the aromatic ring, can improve catalytic reactivity, whereas appropriate enlargement of conjugated aromatic systems results in unchanged activity; 3) the newly designed catalysts are more active than NHPI and NHNI and have catalytic activities comparable to NDHPI and THICA; 4) the ionic-pair supported case is suggested to be a very active catalyst, even towards inert propane, and can be used as a novel model catalyst for further improvements. The present work will be helpful in designing reactive hydroxyimide organocatalysts.

For conventional organic substituents, an almost linear relationship can be established between the para Hammett constants in aqueous solutions and chemical shifts or natural population analysis charges (NPA charges). Based on these correlations, the Hammett constants of six synthesized ionic-pair substituents were estimated via the chemical shifts, which were well in agreement with the results calculated by NPA charges. The para Hammett constants of 89 different ionic-pair substituents (77 anion-cationic and 12 cation-anionic) were therefore calculated in the gas phase based on the density functional theory method. The results show that both the anion-cationic and cation-anionic substituents are electron-withdrawing groups and the different cation–anion combinations could tune the Hammett constants of the ionic-pair substituents in a range from 0.03 to 0.77. Copyright © 2013 John Wiley & Sons, Ltd.

N,N-dihydroxypyromellitimide (NDHPI) and N,N′,N′′-trihydroxyisocyanuric acid (THICA) have been recently demonstrated to act as better carbon-radical-producing catalysts than the popular N-hydroxyphthalimide (NHPI). To gain a mature understanding of these particular catalysts, herein their geometrical, electronic, and thermochemical properties, as well as their catalytic activities, have been systemically investigated by a theoretical analysis. It appears that THICA, unlike NDHPI and NHPI, is unsuitable for solvent-free catalysis or catalysis in aprotic solvents due to its favorable coexistent planar conformer. Besides, the more remarkable catalytic efficiencies of NDHPI and THICA compared to NHPI can be ascribed to the lower barriers and the endothermicity in the H-abstraction processes by their radicals, especially by their multi-radicals which show stronger electron-withdrawing effects. Furthermore, the generation of THICA radicals would be much feasible at high temperature without co-catalysts. This study provides a new perspective towards the rational design of reactive hydroxyimide organocatalysts for industrial applications.

Graphitic carbon nitride (g-C₃N₄) and N-hydroxy compounds can function as a non-metal photocatalytic system to activate O₂ for the selective allylic oxidation under mild conditions, avoiding the employment of any metal derivative or organic oxidizing agents. Interestingly, the novel photocatalytic system affords a remarkably high selectivity towards the formation of aldehydes, especially in the oxidation of toluene. By combining the unique nature of g-C₃N₄ (surface basicity, semiconductor features, high stability) and the remarkable catalytic oxidation reactivity of nitroxyl radicals, this photocatalytic system opens up a mild and efficent access for CH bond activation.

Novel, monodispersed, and well-defined ABA triblock copolymers [poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate)] were synthesized by oxyanionic polymerization with potassium tert-butanoxide as the initiator. Gel permeation chromatography and ¹H-NMR analysis showed that the obtained products were the desired copolymers with molecular weights close to calculated values. Because the poly(dimethylamino ethyl methacrylate) block was pH- and temperature-sensitive, the aqueous solution behavior of the polymers was investigated with ¹H-NMR and dynamic light scattering techniques at different pH values and at different temperatures. The micelle morphology was determined with transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009