SYNTHESIS AND GEOMETRY DETERMINATION OF COFACIAL DIPORPHYRINS - ELECTRON-PARAMAGNETIC-RES SPECTROSCOPY OF DICOPPER DIPORPHYRINS IN FROZEN SOLUTION

被引:137
作者
EATON, SS
EATON, GR
CHANG, CK
机构
[1] MICHIGAN STATE UNIV, DEPT CHEM, E LANSING, MI 48824 USA
[2] UNIV DENVER, DEPT CHEM, DENVER, CO 80208 USA
关键词
D O I
10.1021/ja00297a024
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Frozen solution EPR spectra were obtained for the dicopper complexes of 6 covalently linked diporphyrins whose synthesis is also described. The distance between the Cu atoms in the diporphyrins was determined from the ratio of the intensity of the half-field transitions to the intensity of the allowed transitions and by computer simulation of the spectra. The values obtained by the 2 methods were in good agreement and ranged from 4.1-5.6 .ANG.. The porphyrin planes were parallel within experimental uncertainty. The angle between the interspin vector and the normal to the porphyrin planes (slip angle) was determined by computer simulation of the spectra and values ranged from 20.degree.-45.degree.. For the majority of the diporphyrins the separation between the porphyrin planes was 3.9 .+-. 0.1 .ANG.. In an anthracene pillared diporphyrin the interplanar separation was 4.6 .ANG.. These results were compared with those determined from crystal structures. Although there was no short bond pathway between the 2 Cu atoms, the simulations of the spectra indicated that the absolute value of the copper-copper exchange interaction, J, was > 0.3 cm-1.
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收藏
页码:3177 / 3184
页数:8
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