Water-Triggered Photoinduced Electron Transfer in Acetonitrile–Water Binary Solvent. Solvent Microstructure-Tuned Reactivity of Hydrophobic Solutes

Photoinduced electron transfer and geminate recombination for photoexcited acceptors in a pure donor solvent.

Photoinduced electron transfer and geminate recombination are studied for the systems rhodamine 3B (R3B(+)) and rhodamine 6G (R6G(+)), which are cations, in neat neutral N,N-dimethylaniline (DMA). Following photoexcitation of R3B(+) or R6G(+) (abbreviated as R(+)), an electron is transferred from DMA to give the neutral radical R and the cation DMA(+). Because the DMA hole acceptor is the neat ...

Influence of solvent on photoinduced electron-transfer reaction: time-resolved resonance Raman study.

Time-resolved resonance Raman spectroscopy (TR3) has been used to study the effect of solvent polarity on the mechanism and nature of intermediates formed in photoinduced electron-transfer reaction between triplet flouranil ((3)FL) and tetramethylbenzene (TMB). Comparison of the TR3 spectra in polar, nonpolar, and medium polar media suggests that formation of radical anion due to electron-trans...

Formation of water clusters in a hydrophobic solvent.

Ultrafast charge-transfer-to-solvent dynamics of iodide in tetrahydrofuran. 2. Photoinduced electron transfer to counterions in solution.

The excited states of atomic anions in liquids are bound only by the polarization of the surrounding solvent. Thus, the electron-detachment process following excitation to one of these solvent-bound states, known as charge-transfer-to-solvent (CTTS) states, provides a useful probe of solvent structure and dynamics. These transitions and subsequent relaxation dynamics also are influenced by othe...

Singlet Oxygen Reactivity in Water-rich Solvent Mixtures

The 3-methylindole (3MI) oxygenation sensitized by psoralen (PSO) has been investigated in 100%, 20% and 5% O 2 -saturated water/ dioxane (H 2 O/Dx) mixtures. The lowering of the O 2 * chemical rate when water (k chem 3MI = 1.4 109 M s) is replaced by deuterated water (k chem 3MI = 1.9 108 M s) suggests that hydrogen abstraction is involved in the rate determining step. A high dependence of the...