Selective supramolecular porphyrin/fullerene interactions

被引:377
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
相关论文
共 31 条
[1]  
ATWOOD JL, 1970, NATURE, V368, P229
[2]   Self-consistent molecular Hartree-Fock-Slater calculations - I. The computational procedure [J].
Baerends, E. J. ;
Ellis, D. E. ;
Ros, P. .
CHEMICAL PHYSICS, 1973, 2 (01) :41-51
[3]   Reactions of transition metal complexes with fullerenes (C60, C70, etc.) and related materials [J].
Balch, AL ;
Olmstead, MM .
CHEMICAL REVIEWS, 1998, 98 (06) :2123-2165
[4]   Solubility of C-60 [J].
Beck, MT ;
Mandi, G .
FULLERENE SCIENCE AND TECHNOLOGY, 1997, 5 (02) :291-310
[5]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[6]   AN EMPIRICAL CORRECTION FOR ABSORPTION ANISOTROPY [J].
BLESSING, RH .
ACTA CRYSTALLOGRAPHICA SECTION A, 1995, 51 :33-38
[7]  
*BRUK AN XRAY SYST, 1997, SHELXTL SOFTW REF MA
[8]  
*BRUK AN XRAY SYST, 1997, SAINTPLUS SOFTW REF
[9]  
*BRUNK AN XRAY SYS, 1997, SMART SOFTW REF MAN
[10]   [60]FULLERENE AND TCNQ DONOR-ACCEPTOR CRYSTALS OF OCTAKIS(DIMETHYLAMINO)PORPHYRAZINE [J].
EICHHORN, DM ;
YANG, SL ;
JARRELL, W ;
BAUMANN, TF ;
BEALL, LS ;
WHITE, AJP ;
WILLIAMS, DJ ;
BARRETT, AGM ;
HOFFMAN, BM .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (16) :1703-1704