Synthesis and characterizations of free base and Cu(II) complex of a porphyrin sheet

被引：43

作者：

Nakamura, Yasuyuki ^{[1
]}

Aratani, Naoki ^{[1
]}

Furukawa, Ko ^{[2
]}

Osuka, Atsuhiro ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Sci, Dept Chem, Sakyo Ku, Kyoto 6068502, Japan

[2] Natl Inst Nat Sci, Inst Mol Sci, Okazaki, Aichi 4448585, Japan

来源：

TETRAHEDRON | 2008年 / 64卷 / 50期

基金：

日本学术振兴会;

关键词：

D O I：

10.1016/j.tet.2008.08.072

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Free base porphyrin sheet 5 was prepared by demetalation of zinc complex 1, which was flow more conveniently prepared in 30% yield by oxidation of a mixture of tetraporphyrins, 8, 9, and 11. The H-1 NMR spectrum of 5 shows no indication of an aromatic ring current for the porphyrin rings and evidences the freezing of the pyrrolic NH protons at the most inner and cuter corner positions, both of which contrast sharply with strong aromatic ring currents and rapid NH tautomerism of normal porphyrins. DFT calculations supported the experimental results, suggesting that the enforced planar COT core Causes these unique properties. The free base 5 was transformed into Cu(II) complex 6 that exhibits antiferromagnetic interaction among the Cu(II) ions with J=-1.16 cm(-1). (C) 2008 Elsevier Ltd. All rights reserved.

引用

页码：11433 / 11439

页数：7

共 45 条

[11]

Cyrañski MK, 1998, ANGEW CHEM INT EDIT, V37, P177, DOI 10.1002/(SICI)1521-3773(19980202)37:1/2<177::AID-ANIE177>3.0.CO

[12]

2-H

[13] SYNTHESIS AND GEOMETRY DETERMINATION OF COFACIAL DIPORPHYRINS - ELECTRON-PARAMAGNETIC-RES SPECTROSCOPY OF DICOPPER DIPORPHYRINS IN FROZEN SOLUTION [J].

EATON, SS ;

EATON, GR ;

CHANG, CK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (11) :3177-3184

[14] An expedient synthesis of substituted tetraaryltetrabenzoporphyrins [J].

Finikova, O ;

Cheprakov, A ;

Beletskaya, I ;

Vinogradov, S .

CHEMICAL COMMUNICATIONS, 2001, (03) :261-262

[15]

Frisch M.J., 2004, Gaussian 03

[16]

Revision C.02

[17] SPECTRA OF PORPHYRINS [J].

GOUTERMAN, M .

JOURNAL OF MOLECULAR SPECTROSCOPY, 1961, 6 (01) :138-&

[18]

Graça M, 1999, CHEM COMMUN, P1771

[19] Probing electronic communication in covalently linked multiporphyrin arrays. A guide to the rational design of molecular photonic devices [J].

Holten, D ;

Bocian, DF ;

Lindsey, JS .

ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (01) :57-69

[20] The importance of a β-β bond for long-range antiferromagnetic coupling in directly linked copper(II) and silver(II) diporphyrins [J].

Ikeue, T ;

Furukawa, K ;

Hata, H ;

Aratani, N ;

Shinokubo, H ;

Kato, T ;

Osuka, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (42) :6899-6901

← 1 2 3 4 5 →