期刊
CHEMISTRY-AN ASIAN JOURNAL
卷 2, 期 7, 页码 860-866出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.200700112
关键词
conjugation; host-guest systems; macrocycles; paratropic ring current; porphyrinoids
Anomalous induced magnetic effects were observed in a directly fused square-planar porphyrin sheet 1, in that the protons above the center of the tetraporphyrin core were characteristically shifted downfield in the H-1 NMR spectrum. These observations suggest a rare paratropic ring-current effect around the planar cyclooctatetraene (COT) core of 1. To examine the spatial distribution of the induced magnetic effect, face-to-face dimeric complexes of porphyrin sheet I with bipyridyl-type guest molecules (G1-G3) were prepared, which provided complexation-induced shifts (CISs) of the guest molecules as a neat experimental guide to the distance dependence of the induced magnetic effects in 1. Nucleus-independent chemical shift (NICS) values of 1 were calculated by varying the distance of the probe from the plane of 1. Whereas a simple bell-type profile was estimated for the complex (1)(2)-(G1)(4), the distance profiles of the CIS became increasingly flat for (1)(2)-(G2)(4) and (1)(2)-(G3)(4). Finally, we investigated the paratropic ring-current effect just above the COT core of the complex 1-(G4)(2), which agrees well with the theoretically estimated distance-dependent induced magnetic effect. Consequently, both experimental and theoretical studies on the complexes of porphyrin sheets with guest molecules revealed for the first time a unique distance dependence of the paratropic ring current.
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