Spectroscopic properties of chlorophylls and their derivatives. Influence of molecular structure on the electronic state

Yoshimune Nonomura, Shigeo Igarashi, Naoki Yoshioka, Hidenari Inoue

研究成果: Article査読

37 被引用数 (Scopus)

抄録

The spectroscopic properties of chlorophylls (Mg-Chl a and H2-Chl a), metallochlorophyll a and b (M-Chl a and b, M = Ni, Cu and Zn), zinc(II) pyromethylpheophorbide a (Zn-PMP a) and zinc(II) chlorin e6 trimethyl ester (Zn-Chl e6 TME) were studied by circular dichroism (CD), magnetic circular dichroism (MCD), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The electronic absorption spectra were assigned in terms of the spectral analysis of CD and MCD. The absorption maximum of the Qy band varied linearly with the electronegativity of the central metal M and the energy level of the macrocyclic π orbitals in M-Chl a. The semiempirical MO calculation demonstrated that the deviation of H2-Chl a from the general trend is induced by rising of the energy levels of next HOMO and second next HOMO in H2-Chl a. A comparison of the UV-VIS and MCD spectral data in zinc(II) chlorophylls revealed that the substituents on the pyrrole β position and the ring V govern the position of the Q and B bands. The spectroscopic behavior was explained on the basis of the energy level of the macrocyclic π orbitals calculated by the conventional MO method.

本文言語English
ページ(範囲)155-166
ページ数12
ジャーナルChemical Physics
220
1-2
DOI
出版ステータスPublished - 1997 7 15

ASJC Scopus subject areas

  • 物理学および天文学(全般)
  • 物理化学および理論化学

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