A microreaction system for organic photoreactions was developed, and the processes of diastereo-differentiating photosensitized reaction, photocatalytic oxidation and reduction of organic compounds, and amine N-alkylation were examined in microspace. These model reactions proceeded very rapidly with considerably large photonic efficiencies because of some distinct properties of microreactors for photoreactions, such as higher spatial illumination homogeneity and better light penetration through the entire reactor depth, and large surface-to-volume ratio in comparison with large-scale batch reactors. These results suggest feasibility of microreaction systems on organic photoreactions.
Laser-induced fluorescence (LIF) excitation, UV-UV hole burning, and single vibronic level fluorescence (SVLF) spectra of jet-cooled o-fluoroanisole (o-FA) were measured. The most intense lowest-frequency band at 36 612 cm(-1) was assigned to the origin band of the most stable trans conformer. The UV-UV hole-burning spectrum demonstrated that the prominent bands in the LIF excitation spectrum were responsible for the trans conformer. The metastable non-planar conformer was not observed in the spectra. The vibrational band assignments were performed with the aid of quantum chemical calculations at the B3LYP/cc-pVTZ and CIS/6-311G(d,p) levels. The precise analysis of the SVLF spectra indicated that strong vibrational mixing through the Duschinsky effect and the Fermi resonance occurs in the S(1) state.
Photocatalytic reduction of benzaldehyde and nitrotoluene in microspace was investigated by using a microreactor with immobilized titanium dioxide. Advantages of a photocatalytic microreaction system which has a remarkably large surface-to-volume ratio have been examined.
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