Self-assembly of a porphyrin array via the molecular recognition approach: Synthesis and properties of a cyclic zinc(II) porphyrin trimer based on coordination and hydrogen bonding

C. Ikeda, Y. Tanaka, T. Fujihara, Y. Ishii, T. Ushiyama, K. Yamamoto, Naoki Yoshioka, H. Inoue

Research output: Contribution to journalArticle

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Abstract

Self-assembly of [5-(pyrazol-4-yl)-10,20-bis(p-tolyl)-15-(2-ethoxycarbonylphenyl) porphyrinato]-zinc(II) designed to have both a coordination site and a hydrogen bonding site, leads to a stable cyclic trimer array where coordination of the pyrazole nitrogen to the zinc(II) ion as well as hydrogen bonding between carbonyl oxygen and pyrazole NH holds each zinc(H) porphyrin. The recognition event for pyrazole has been confirmed preliminarily in the model studies using [5-(2-ethoxycarbonylphenyl)tris(p-tolyl)porphyrinato]-zinc(II) (3). The zinc(II) porphyrin 3 has large affinity for pyrazole due to the hydrogen bond between pyrazole and the 2-ethoxycarbonyl group in addition to the coordination bonding accompanied by the conformational change of the ethoxycarbonyl group in the coordination process. The 1H NMR, IR, and UV-vis spectra of 1 and its ESI-MS and VPO measurements have revealed the cyclic trimer structure with an overall association constant of 6.0 x 1013 M-2 at 22 °C. The contribution of the hydrogen bond to the total free energy change in trimer formation is estimated to be 7.5 kcal/mol based on a reference trimer system without a hydrogen bonding site. The trimer geometry causes characteristic exitonic interaction between porphyrin units to yield a broad Soret band which is deconvoluted into four components by UV-vis and MCD spectral analyses. Electrochemical measurements have shown that only the first ring-oxidation process proceeds stepwise in the trimer.

Original languageEnglish
Pages (from-to)3395-3405
Number of pages11
JournalInorganic Chemistry
Volume40
Issue number14
DOIs
Publication statusPublished - 2001 Jul 2

Fingerprint

Molecular recognition
Porphyrins
trimers
porphyrins
Self assembly
self assembly
Zinc
Hydrogen bonds
zinc
hydrogen
synthesis
hydrogen bonds
Free energy
Nitrogen
Nuclear magnetic resonance
affinity
pyrazole
Association reactions
Oxygen
Oxidation

ASJC Scopus subject areas

  • Inorganic Chemistry

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Self-assembly of a porphyrin array via the molecular recognition approach : Synthesis and properties of a cyclic zinc(II) porphyrin trimer based on coordination and hydrogen bonding. / Ikeda, C.; Tanaka, Y.; Fujihara, T.; Ishii, Y.; Ushiyama, T.; Yamamoto, K.; Yoshioka, Naoki; Inoue, H.

In: Inorganic Chemistry, Vol. 40, No. 14, 02.07.2001, p. 3395-3405.

Research output: Contribution to journalArticle

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