Recognition of α-amino acid esters by zinc porphyrin derivatives via coordination and hydrogen bonding interactions. Evidence for two-point fixation from thermodynamic and induced circular dichroism spectroscopic studies

Tadashi Mizutani, Tadashi Ema, Takashi Yoshida, Yasuhisa Kuroda, Hisanobu Ogoshi

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Abstract

Association constants between [trans-5,15-bis(2-hydroxy-1-naphthyl)-2,3,7,8,12,13,17,18-octaethylporphyrinato] -zinc(II) (1) and a series of α-amino acid esters (RCHNH2CO2CH3) were determined in chloroform by use of a UV-vis titration method. Association constants increased in the order Ala-OMe <Gly-OMe <Val-OMe <Leu-OMe, showing a preference for bulky amino acid esters. Contributions from the metal coordination and hydrogen bonding interactions to the total free energy change were estimated by use of reference compounds having no hydrogen bonding site. The free energy change for the binding of Leu-OMe to 1 in chloroform at 15°C was -5.3 kcal/mol, which was separated into two contributions, (1) the metal coordination interaction ΔGMC = -3.8 kcal/mol and (2) the hydrogen bonding interaction ΔGHB = -1.5 kcal/mol. Circular dichroism (CD) induced in the porphyrin Soret band of 1 by complexation with optically active amino acid esters was of the split type for all the amino acid esters examined, whereas induced CD of a reference host, [trans-5,15-bis(2-methoxy-1-naphthyl)-2,3,7,8,12,13,-17,18- octaethylporphyrinato]zinc(II) (2), was reduced in intensity and not of the split type. We found that the fixation of the carbonyl group of the guest by two-point recognition caused marked enhancements in induced CD. We suggest that the induced CD of 1 was caused by the coupling between the magnetic transition dipole moment of the carbonyl group of guest and the electric transition dipole moment of the Soret band of host.

Original languageEnglish
Pages (from-to)2072-2077
Number of pages6
JournalInorganic Chemistry
Volume32
Issue number10
Publication statusPublished - 1993
Externally publishedYes

Fingerprint

porphyrins
dichroism
amino acids
esters
Hydrogen bonds
Esters
zinc
Thermodynamics
Derivatives
Amino Acids
thermodynamics
Dipole moment
hydrogen
Chloroform
chloroform
Free energy
Zinc
dipole moments
Metals
free energy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Recognition of α-amino acid esters by zinc porphyrin derivatives via coordination and hydrogen bonding interactions. Evidence for two-point fixation from thermodynamic and induced circular dichroism spectroscopic studies. / Mizutani, Tadashi; Ema, Tadashi; Yoshida, Takashi; Kuroda, Yasuhisa; Ogoshi, Hisanobu.

In: Inorganic Chemistry, Vol. 32, No. 10, 1993, p. 2072-2077.

Research output: Contribution to journalArticle

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T1 - Recognition of α-amino acid esters by zinc porphyrin derivatives via coordination and hydrogen bonding interactions. Evidence for two-point fixation from thermodynamic and induced circular dichroism spectroscopic studies

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