Femtosecond spectroscopy on the photochemistry of ortho-nitrotoluene

文献情報

出版日 2010-07-01

DOI 10.1039/C004025H

インパクトファクター 3.676

著者

T. Schmierer, S. Laimgruber, K. Haiser, K. Kiewisch, J. Neugebauer

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要旨

The photo tautomerisations of ortho-nitrotoluene (oNT) and its methylated derivative ortho-ethylnitrobenzene (oENB) have been studied by means of femtosecond spectroscopy and (TD)-DFT computations. In UV/Vis transient absorption spectroscopy a band peaking at 400 nm is seen to rise in a bi-modal manner with time constants of 1–10 ps and 1500 ps. Femtosecond stimulated Raman experiments clearly identify aci-nitro forms as the spectroscopic carriers of the 400 nm band. The assignment of the Raman spectra is based on TD-DFT computations. The quantum yields of the aci-nitro forms after 3 ns are 0.08 (oNT) and 0.3 (oENB). The aci-nitro forms are formed via a singlet channel (1–10 ps) and a triplet channel (1500 ps). There are indications that the triplet channel involves a bi-radical intermediate. In between 3 ns and 1 ms the spectrum of the aci-nitro form shifts from 400 to 390 nm. This could indicate a tautomerisation from Z-aci-nitro to an E form.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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