Theoretical study of the Q and B bands of free-base, magnesium, and zinc porphyrins, and their derivatives

被引:175
作者
Hashimoto, T [1 ]
Choe, YK [1 ]
Nakano, H [1 ]
Hirao, K [1 ]
机构
[1] Univ Tokyo, Grad Sch Engn, Dept Appl Chem, Tokyo 1138656, Japan
关键词
D O I
10.1021/jp984807d
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The multireference Moller-Plesset perturbation (MRMP) theory with complete active space self-consistent field (ICASSCF) reference functions is applied to the study of the Q and B bands of free-base, magnesium, and zinc porphyrins and their derivatives. The Q band of free-base porphyrin is so weak because the transition is pseudoparity-forbidden because of the alternancy symmetry. The Q band in the visible region can be intensified if the pairing property is broken. This is achieved by various chemical modifications to the basic structure of free-base porphyrin such as external substituents, changes in conjugation pathway, and change in central substituent. The intensity and color of the Q band as well as the macrocyclic porphyrin skeleton are perturbed to a greater or lesser extent by various chemical modifications. Insertion of aza groups in meso position leads to the shrinking of the size of the central hole, whereas hydrogenation to the exo double bond of pyrrole rings expands the central hole. Substitution of nitrogen atoms for meso carbon atoms significantly intensifies the oscillator strength of the higher energy side transition of the Q band with the peak position unchanged. Ring reduction widens the splitting of two peaks of the Q band, giving rise to the characteristically strong far-red band and the weaker visible band. Changes from metal-free to metalloporphyrins have a less dramatic effect on the spectra.
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页码:1894 / 1904
页数:11
相关论文
共 31 条
[1]   ELECTRON CORRELATION IN TETRAPYRROLES - AB-INITIO CALCULATIONS ON PORPHYRIN AND THE TAUTOMERS OF CHLORIN [J].
ALMLOF, J ;
FISCHER, TH ;
GASSMAN, PG ;
GHOSH, A ;
HASER, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (42) :10964-10970
[2]   REDETERMINATION OF STRUCTURE OF PORPHINE [J].
CHEN, BML ;
TULINSKY, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (12) :4144-&
[3]  
Dolphin D., 1978, PORPHYRINS, VIII
[5]   SPECTRAL-LUMINESCENT AND QUANTUM-CHEMICAL STUDY OF AZAPORPHYRIN MOLECULES [J].
DVORNIKOV, SS ;
KNYUKSHTO, VN ;
KUZMITSKY, VA ;
SHULGA, AM ;
SOLOVYOV, KN .
JOURNAL OF LUMINESCENCE, 1981, 23 (3-4) :373-392
[6]   PORPHYRINS .17. VAPOR ABSORPTION SPECTRA AND REDOX REACTIONS - TETRAPHENYLPORPHINS AND PORPHIN [J].
EDWARDS, L ;
DOLPHIN, DH ;
GOUTERMAN, M ;
ADLER, AD .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1971, 38 (01) :16-+
[7]   TOWARD A SYSTEMATIC MOLECULAR-ORBITAL THEORY FOR EXCITED-STATES [J].
FORESMAN, JB ;
HEADGORDON, M ;
POPLE, JA ;
FRISCH, MJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (01) :135-149
[8]   Theoretical comparative study of free base porphyrin, chlorin, bacteriochlorin, and isobacteriochlorin: Evaluation of the potential roles of ab initio Hartree-Fock and density functional theories in hydrophorphyrin chemistry [J].
Ghosh, A .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (16) :3290-3297
[9]   STUDY OF THE EFFECTS OF SUBSTITUTION ON THE ABSORPTION SPECTRA OF PORPHIN [J].
GOUTERMAN, M .
JOURNAL OF CHEMICAL PHYSICS, 1959, 30 (05) :1139-1161
[10]   Coupled-cluster calculations of the electronic excitation spectrum of free base porphin in a polarized basis [J].
Gwaltney, SR ;
Bartlett, RJ .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (16) :6790-6798