Ionization of cyclic aromatic amines by free electron transfer: products are governed by molecule flexibility |
| |
Authors: | Brede Ortwin Maroz Andrej Hermann Ralf Naumov Sergej |
| |
Institution: | Interdisciplinary Group Time-Resolved Spectroscopy, University of Leipzig, Permoserstrasse 15, 04303 Leipzig, Germany. brede@mpgag.uni-leipzig.de |
| |
Abstract: | The bimolecular electron transfer from secondary aromatic amines to parent radical cations of nonpolar solvents such as alkanes and alkyl chlorides results in the synchronous formation of amine radical cations as well as aminyl radicals, in comparable amounts. If as for cyclic aromatic amines (c-Ar(2)NH) the intramolecular bending motion around the amine group is restricted in varying degrees (acridane, phenothiazine) or completely prevented (carbazole), then this picture is modified. In the free electron transfer, the completely rigid carbazole yields exclusively amine radical cations. Acridane exhibits preferred radical cations, but phenothiazine with the more flexible six-membered ring involving sulfur as a further heteroatom follows the common two-product rule; see above. The phenomenon is reasoned by a peculiarity in the bimolecular free electron transfer where after diffusional approach the actual electron jump proceeds in the ultrashort time range. Therefore, it reflects femtosecond molecular motions which, in the case of free mobility, continuously pass through different molecule conformers, combined with fluctuation of the electrons of the responsible molecular n-orbitals. The rigid systems, however, do not show this effect because of a nonexistent bending motion. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|