期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 65, 期 21, 页码 6826-6836出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo000570h
关键词
-
The spontaneous assembly of aromatic cation-radicals (D+.) with the parent donor (D) to afford the paramagnetic dimer (D)(2)(+.) is accompanied by a dramatic color change. For example, spectral (UV-vis and ESR) and X-ray crystal structure analyses establish the molecular association of octamethylbiphenylene cation-radical with its neutral counterpart to produce the mixed-valence or dimeric cation-radical in which the positive charge is completely delocalized over both aromatic moieties. The use of the sterically hindered cation-radicals confirms the new spectral or charge-resonance (CR) band to result in dimeric cation-radicals in which the intermolecular separation occurs at an optimum distance allowed by van der Waals contacts. The striking similarities between the classical donor/acceptor (EDA) complexes and the dimeric cation-radicals (D)(2)(+.) (both in terms of the geometrical requirement as well as the appearance of new absorption bands) suggest that the latter can be considered as particular examples of Mulliken's charge-transfer complexes in which the positive charge is completely (equally) delocalized over both donor (D) and acceptor (D+.).
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据