Directly meso-meso linked porphyrin rings:: Synthesis, characterization, and efficient excitation energy hopping

被引:141
作者
Nakamura, Y
Hwang, IW
Aratani, N
Ahn, TK
Ko, DM
Takagi, A
Kawai, T
Matsumoto, T
Kim, D [1 ]
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] Kyoto Univ, Grad Sch Sci, Dept Chem, Sakyo Ku, Kyoto 6068502, Japan
[4] Japan Sci & Technol Agcy, Core Res Evolut Sci & Technol, Sakyo Ku, Kyoto 6068502, Japan
[5] Osaka Univ, ISIR, CREST, JST Agcy, Osaka 5670047, Japan
关键词
D O I
10.1021/ja045254p
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5,10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple H-1 NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the 1H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Forster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 +/- 2 fs)(-1), CZ6 (342 +/- 59 fs)(-1), and CZ8 (236 +/- 31 fs)(-1), which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.
引用
收藏
页码:236 / 246
页数:11
相关论文
共 78 条
  • [31] Cyclic [6]- and [8]paraphenylacetylenes
    Kawase, T
    Darabi, HR
    Oda, M
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1996, 35 (22): : 2664 - 2666
  • [32] Photophysical properties of directly linked linear porphyrin arrays
    Kim, D
    Osuka, A
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (42) : 8791 - 8816
  • [33] Photophysical properties of long rodlike meso-meso-linked zinc(II) porphyrins investigated by time-resolved laser spectroscopic methods
    Kim, YH
    Jeong, DH
    Kim, D
    Jeoung, SC
    Cho, HS
    Kim, SK
    Aratani, N
    Osuka, A
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (01) : 76 - 86
  • [34] Dynamic equilibrium unfolding pathway of human tumor necrosis factor-α induced by guanidine hydrochloride
    Kim, YR
    Hahn, JS
    Hong, H
    Jeong, W
    Song, NW
    Shin, HC
    Kim, D
    [J]. BIOCHIMICA ET BIOPHYSICA ACTA-PROTEIN STRUCTURE AND MOLECULAR ENZYMOLOGY, 1999, 1429 (02): : 486 - 495
  • [35] The crystal structure of the light-harvesting complex II (B800-850) from Rhodospirillum molischianum
    Koepke, J
    Hu, XC
    Muenke, C
    Schulten, K
    Michel, H
    [J]. STRUCTURE, 1996, 4 (05) : 581 - 597
  • [36] Formation and properties of cyclo[6]pyrrole and cyclo[7]pyrrole
    Köhler, T
    Seidel, D
    Lynch, V
    Arp, FO
    Ou, ZP
    Kadish, KM
    Sessler, JL
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (23) : 6872 - 6873
  • [37] Krömer J, 2000, ANGEW CHEM INT EDIT, V39, P3481
  • [38] Light-harvesting macroring accommodating a tetrapodal ligand based on complementary and cooperative coordinations
    Kuramochi, Y
    Satake, A
    Kobuke, Y
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (28) : 8668 - 8669
  • [39] Synthesis and self-assembly of giant porphyrin discs
    Lensen, MC
    van Dingenen, SJT
    Elemans, JAAW
    Dijkstra, HP
    van Klink, GPM
    van Koten, G
    Gerritsen, JW
    Speller, S
    Nolte, RJM
    Rowan, AE
    [J]. CHEMICAL COMMUNICATIONS, 2004, (07) : 762 - 763
  • [40] Aided self-assembly of porphyrin nanoaggregates into ring-shaped architectures
    Lensen, MC
    Takazawa, K
    Elemans, JAAW
    Jeukens, CRLPN
    Christianen, PCM
    Maan, JC
    Rowan, AE
    Nolte, RIM
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (04) : 831 - 839