期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 126, 期 39, 页码 12604-12613出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja0305959
关键词
-
A nitronyl-nitroxide (NIT) biradical D-NIT2 linked by a single double bond has been engineered and investigated in the solid state by a combination of X-ray diffraction, magnetic susceptibility measurement, EPR, as well as solid-state H-1 and C-13 NMR spectroscopies, and experimental electron density distribution. All techniques reveal that a double bond is a very efficient coupling unit for exchange interactions between two radical moieties. Using a Bleaney-Bowers model dinner (H = -JS(1)S(2))(1) a singlet-triplet energy gap of J = -460 K was found with the singlet state being the ground state. This very strong intramolecular interaction was confirmed by EPR measurements in CH2Cl2 solution (6 10(-4) M) or dispersed in a polymer matrix at low concentration. In keeping with these unusual interactions, solid-state NMR signals of the biradical were found to be considerably less shifted than those found for related monoradicals. Temperature-dependent solid-state C-13 NMR spectra of D-NIT2 confirmed the very strong intramolecular coupling constant (J = -504 K). The electron density distribution of D-NIT2 was measured by high resolution X-ray diffraction, which also revealed that this biradical is an ideally conjugated system. The in-depth characterization includes the deformation maps and the observed electron density ellipticities, which exhibit a pronounced sigma-pi character of the O-N-C=C-N-O cores in keeping with an efficient electronic delocalization along the alkene spacer.
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