Selective supramolecular porphyrin/fullerene interactions

被引:375
作者
Boyd, PDW
Hodgson, MC
Rickard, CEF
Oliver, AG
Chaker, L
Brothers, PJ
Bolskar, RD
Tham, FS
Reed, CA
机构
[1] Univ Auckland, Dept Chem, Auckland, New Zealand
[2] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA
关键词
D O I
10.1021/ja992165h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Naturally assembling cocrystallates of C-60 and C-70 fullerenes with tetraphenylporphyrins (H2TPP . C-60. 3 toluene, 1; H2T3,5-dibutylPP . C-60, 2; H2T3,5-dimethylPP . 1.5C(60). 2 toluene, 3; H2TpivPP . C-60, 4; H2T3,5-dimethylPP . C-70. 4 toluene, 5; ZnTPP . C-70, 6; NiT4-methylPP . 2C(70). 2 toluene, 7) show unusually short porphyrin/fullerene contacts (2.7-3.0 Angstrom) compared with typical pi-pi interactions (3.0-3.5 Angstrom). In the C-60 structures,an electron-rich, 6:6 ring juncture, C-C bond lies over the center of the porphyrin ring. In the C-70 structures, the ellipsoidal fullerene makes porphyrin contact at its equator rather than its poles; a carbon atom from three fused six-membered rings lies closest to the center of the porphyrin. These structures provide an explanation for the manner in which tetraphenylporphyrin-appended silica stationary phases effect the chromatographic separation of fullerenes. The interaction of the curved pi surface of a fullerene with the planar pi surface of a porphyrin, without the need for matching convex with concave surfaces, represents a new recognition element in supramolecular chemistry. NMR measurements show that this interaction persists in toluene solution, suggesting a simple way to assemble van der Waals complexes of donor-acceptor chromophores.
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页码:10487 / 10495
页数:9
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