High-Pressure ESR Spectroscopy: On the Rotational Motion of Spin Probes in Pressurized Ionic Liquids.

We report high-pressure (up to 50 MPa) ESR-spectroscopic investigations on the rotational correlation times of the nitroxide radicals 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPOL), and 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl (ATEMPO) in the ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF4), 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), 1-methyl-3-octylimidazolium tetrafluoroborate (omimBF4), and 1-methyl-3-octylimidazolium hexafluorophosphate (omimPF6). The activation volumes (38.5-56.6 Å3) determined from pressure dependent rotational diffusion coefficients agree well with the pressure dependent viscosities of the ionic liquids. Experimentally, the fractional exponent of the generalized Stokes-Einstein-Debye relation is found to be close to one.

A three-component reaction by photoinduced electron transfer mechanism with N-protected pyrroles as neutral carbon nucleophiles.

A new photoinduced three-component reaction between a cyanoarene, an alkene and an N-protected pyrrole has been developed. This reaction extended the scope of the photo-NOCAS reaction by introducing pyrrole as a neutral carbon-centered nucleophile. The cyanoarenes used include tetracyanobenzene (TCB), 2,3,5,6-tetrafluoro-1,4-dicyanobenzene (TFDCB) and 1,4-dicyanobenzene (DCB). N-Methyl, N-phenyl and N-Boc pyrroles are suitable nucleophiles in the reaction. Taking advantage of the strong electron acceptor ability of the singlet excited TCB, a wide range of alkenes, including the highly electron deficient 4-fluoro-, 4-chloro-, 2,3,4,5,6-pentafluorostyrenes and N-methylmaleimide take part in this reaction, leading to the simultaneous 1,2-diarylation of the alkene and the regioselective 2-alkylation of the pyrrole ring via sequential formation of two new C-C bonds between the three reactants.

Recalling the appropriate representation of electronic spectra.

This paper presents a critical discussion on the representation of UV-vis-NIR light absorption and fluorescence emission spectra of polyatomic molecules in liquid solution. A general overview how to handle the experimental spectra in order to extract physical data from them is presented together with some simulations to show the errors that can arise from unfortunate manipulation.