Resonance Raman spectroscopic investigation of directly linked Zinc(II) porphyrin linear arrays

被引:23
作者
Jeong, DH
Yoon, MC
Jang, SM
Kim, D [1 ]
Cho, DW
Yoshida, N
Aratani, N
Osuka, A
机构
[1] Yonsei Univ, Ctr Ultrafast Opt Characterist Control, Seoul 120749, South Korea
[2] Yonsei Univ, Dept Chem, Seoul 120749, South Korea
[3] Seonam Univ, Dept Chem, Namwon 590711, South Korea
[4] Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan
关键词
D O I
10.1021/jp0132331
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
We have investigated the resonance Raman (RR) spectra of the directly linked porphyrin arrays in order to elucidate the relationship between excitonic interactions and molecular geometry depending on the number of pigments in the arrays. The RR spectra obtained by photoexcitation at the high-energy exciton Soret bands in the arrays are mainly composed of Raman modes localized on the constituent porphyrin monomers. In contrast, the RR spectra of the arrays with photoexcitation at the low-energy exciton split Soret bands reveal some characteristic Raman bands arising from strong excitonic interactions between the adjacent porphyrins in the arrays. Based on the RR measurements of the isotope labeled analogues and the normal-mode analysis of the dimer, it is suggested that the photoexcitation at the high-energy Soret band produces an electronically excited state largely localized within a monomer unit and that at the low-energy exciton split Soret band the excited state is in a way delocalized throughout the array. Normal mode calculation revealed that some of the RR bands of Z2 arise from vibrational splitting by dimeric interactions. Phonon-like behaviors were observed for some C-m-C-m stretching modes of the arrays, which is ascribed to enhanced polarizability induced by phenyl group movement. Collectively, our data from RR spectroscopic measurements as well as the normal-mode analysis provide a picture of the exciton coupling in relation to the molecular structure of the directly linked linear porphyrin arrays.
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收藏
页码:2359 / 2368
页数:10
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