title: Experimental and theoretical investigations into the paratropic ring current of a porphyrin sheet.
abstract: 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 1H 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 1 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.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Nakamura
authors.forename: Naoki
authors.initials: N
authors.lastname: Aratani
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
mesh_terms: D019281:Dimerization; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015335:Molecular Probes; D011166:Porphyrins / Q000737:chemistry*
chemical_list: D015335:Molecular Probes; D011166:Porphyrins