Solvation heterogeneity in ionic liquids as demonstrated by photo-chemical reactions

It has been recognised that ionic liquids (ILs) with long alkyl-chains have a segregated structure due to the inhomogeneous distribution of polar parts and non-polar parts. This inhomogeneity of ILs brings about unique solvation phenomena of solute molecules dissolved in ILs. We have investigated various solvation-state selective phenomena by using laser spectroscopic techniques such as solvation state selective vibrational spectroscopy, translational and rotational dynamics of small molecules in ILs, and solvation state selective fundamental chemical reactions. In this paper, we have reviewed an intramolecular electron transfer (ET) reaction in the Marcus inverted region of N,N-dimethyl-p-nitroaniline and an intramolecular proton transfer (IPT) reaction in 4′-N,N-diethylamino-3-hydroxyflavone as examples of chemical reactions affected by unique solvation in ILs.

Glycosidic linkage, N-acetyl side-chain, and other structural properties of methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-β-D-mannopyranoside monohydrate and related compounds

The crystal structure of methyl 2-acetamido-2-deoxy-β-D-glycopyranosyl-(1→4)-β-D-mannopyranoside monohydrate, C15H27NO11·H2O, was determined and its structural properties compared to those in a set of mono- and disaccharides bearing N-acetyl side-chains in βGlcNAc aldohexopyranosyl rings. Valence bond angles and torsion angles in these side chains are relatively uniform, but C—N (amide) and C—O (carbonyl) bond lengths depend on the state of hydrogen bonding to the carbonyl O atom and N—H hydrogen. Relative to N-acetyl side chains devoid of hydrogen bonding, those in which the carbonyl O atom serves as a hydrogen-bond acceptor display elongated C—O and shortened C—N bonds. This behavior is reproduced by density functional theory (DFT) calculations, indicating that the relative contributions of amide resonance forms to experimental C—N and C—O bond lengths depend on the solvation state, leading to expectations that activation barriers to amide cis–trans isomerization will depend on the polarity of the environment. DFT calculations also revealed useful predictive information on the dependencies of inter-residue hydrogen bonding and some bond angles in or proximal to β-(1→4) O-glycosidic linkages on linkage torsion angles ϕ and ψ. Hypersurfaces correlating ϕ and ψ with the linkage C—O—C bond angle and total energy are sufficiently similar to render the former a proxy of the latter.

A Preliminary First Principle Study on Photochromism of Diarylethene Molecules

Photochromism in some diarylethene molecules have been studied by using hybrid density functional theory using the ground state energy consideration. In particular, B3LYP functional and all electron basis set 6-311G (2d,2p) as implemented in Gaussian09 suites of program has been used to investigate the energy difference of two stable isomers of stilbene, azobenzene, cyclooctane, and 1,2, dimethylcyclohexane molecules. The energy difference is corroborated to calculate the frequencies of photons that are required to induce photochromism in these molecules in vacuum and in solvation state. The study found that the molecules exhibit photochromism at various frequency range from infra-red to ultraviolet. The binding energy per atom, charge distribution, HOMO-LUMO (Highest Occupied Molecular Orbital and Lowest Unoccupied Molecular Orbital) gap are also calculated for all the molecules in vacuum, water and ethanol solvent. The results obtained are in accordance with the experimental observations.

Recent Advances in NMR: Aggregation, Solvation, and Dynamics of Selected Organolithium Compounds

Nuclear magnetic resonance (NMR) spectroscopy is the most widely used analytical technique to study the structure and dynamics of organolithium compounds, which are the most popular reagents in organic synthesis due to their great diversity and high reactivity. The main strength of this method is that it allows direct analysis in solution of the aggregation, dynamic, and solvation state of reactive intermediates. In this review, we present the NMR tools (nD) involving the 6Li isotope and DOSY experiments with internal references and illustrate their contribution in the structural and dynamic characterization of organolithium compounds in solution through some selected example.1 Introduction2 Advantages of the 6Li isotope3 NMR Experiments Involving the 6Li Isotope4 Diffusion Ordered NMR Experiments5 Application of NMR to the Structural Characterization of Organolithium Species6 Conclusion

Effect of the solvation state of electron in dissociative electron attachment reaction in aqueous solutions

Dissociative electron attachment induced by prehydrated electron is observed by using multichannel transient absorption measurements at the picosecond range.