Mechanism of induced circular dichroism of amino acid ester-porphyrin supramolecular systems. implications to the origin of the circular dichroism of hemoprotein

Tadashi Mizutani, Tadashi Ema, Takashi Yoshida, Thomas Renné, Hisanobu Ogoshi

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59 Citations (Scopus)

Abstract

Circular dichroism (CD) spectra of the complexes between metalloporphyrins and chiral amino acid derivatives exhibited either split type induced CD or single peak induced CD in the Soret region depending on the host-guest combination. Systematic studies on the complexation of amino acid derivatives by porphyrin hosts indicate that intermolecular hydrogen bonding to the carbonyl group of the guest is necessary for the split type induced CD to occur. Molecular orbital calculations of the rotational strength of a porphyrin-amino acid ester complex by the MNDO method predict that the ICD of porphyrin-amino acid ester complexes is determined by the relative geometry of the carbonyl group and the porphyrin plane. The relative geometry of the chromophores expected from the X-ray crystallographic analysis of a complex between leucine methyl ester and a similar host then gives split type induced CD, in agreement with experiment. These experimental and theoretical results indicate that the coupling between the magnetic transition dipole moment (mj) and the electric transition dipole moment (μj) of a carbonyl group and the electric transition dipole moment (μj) of the porphyrin Soret band makes an important contribution to the observed induced CD.

Original languageEnglish
Pages (from-to)3558-3566
Number of pages9
JournalInorganic Chemistry
Volume33
Issue number16
Publication statusPublished - 1994
Externally publishedYes

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Porphyrins
porphyrins
dichroism
amino acids
esters
Esters
Dipole moment
Amino Acids
dipole moments
Metalloporphyrins
Derivatives
Orbital calculations
Geometry
Molecular orbitals
Chromophores
leucine
Complexation
geometry
Hydrogen bonds
chromophores

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Mechanism of induced circular dichroism of amino acid ester-porphyrin supramolecular systems. implications to the origin of the circular dichroism of hemoprotein. / Mizutani, Tadashi; Ema, Tadashi; Yoshida, Takashi; Renné, Thomas; Ogoshi, Hisanobu.

In: Inorganic Chemistry, Vol. 33, No. 16, 1994, p. 3558-3566.

Research output: Contribution to journalArticle

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