A stepwise electron-transfer relay mimicking the primary charge separation in bacterial photosynthetic reaction center

被引:112
作者
Osuka, A
Marumo, S
Mataga, N
Taniguchi, S
Okada, T
Yamazaki, I
Nishimura, Y
Ohno, T
Nozaki, K
机构
[1] INST LASER TECHNOL,OSAKA 550,JAPAN
[2] OSAKA UNIV,FAC ENGN SCI,DEPT CHEM,TOYONAKA,OSAKA 560,JAPAN
[3] OSAKA UNIV,EXTREME MAT RES CTR,TOYONAKA,OSAKA 560,JAPAN
[4] HOKKAIDO UNIV,FAC ENGN,DEPT CHEM PROC ENGN,SAPPORO,HOKKAIDO 060,JAPAN
[5] OSAKA UNIV,FAC SCI,DEPT CHEM,TOYONAKA,OSAKA 560,JAPAN
关键词
D O I
10.1021/ja9520676
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis and excited-state dynamics are described for zinc-methylenechlorin-porphyrin-pyromellitimide triads, ZC-HP-I and ZC-ZP-I, and related dyads ZC-HP, ZC-ZP, HP-I, and ZP-I, where ZC, HP, ZP, and I indicate a zinc-methylenechlorin, a free-base porphyrin, a zinc-porphyrin, and pyromellitimide, respectively. In the steady-state fluorescence spectra of ZC-HP, ZC-HP-I, ZC-ZP, and ZC-ZP-I, only the emission from ZC is commonly observed, indicating efficient intramolecular singlet-singlet excitation energy transfer from HP or ZP to ZC. ZC-HP-I undergoes a stepwise electron-transfer relay: (1)(ZC)*-HP-1 --> (ZC)(+)-(HP)(-)-I --> (ZC)(+)-HP-(I)(-) with overall quantum yields of 0.70 and 0.07 in THF and DMF, respectively. In ZC-ZP-I, a pre-formed equilibrium between (1)(ZC)*-ZP-I and (ZC)(+)-(ZP)(-)-I is followed by a rapid charge-shift reaction to provide a secondary ion-pair state (ZC)(+)-ZP-(I)(-) with the overall quantum yield of 0.90 and 0.47 in THF and DMF, respectively. The intermediate ion-pair state (ZC)(+)-(ZP)(-)-I is stabilized enough so as to be clearly detected in DMF, while it is slightly higher in energy than (1)(ZC)* in THF, rendering its detection difficult.
引用
收藏
页码:155 / 168
页数:14
相关论文
共 73 条
  • [1] STRUCTURE OF THE REACTION CENTER FROM RHODOBACTER-SPHAEROIDES R-26 - THE COFACTORS .1.
    ALLEN, JP
    FEHER, G
    YEATES, TO
    KOMIYA, H
    REES, DC
    [J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1987, 84 (16) : 5730 - 5734
  • [2] [Anonymous], 1988, Photoinduced Electron Transfer, Part A
  • [3] [Anonymous], 1988, Photoinduced electron transfer, part D
  • [4] MODELING LONG-RANGE PHOTOSYNTHETIC ELECTRON-TRANSFER IN RIGIDLY BRIDGED PORPHYRIN QUINONE SYSTEMS
    ANTOLOVICH, M
    KEYTE, PJ
    OLIVER, AM
    PADDONROW, MN
    KROON, J
    VERHOEVEN, JW
    JONKER, SA
    WARMAN, JM
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (05) : 1933 - 1941
  • [5] THE ACCESSORY BACTERIOCHLOROPHYLL - A REAL ELECTRON CARRIER IN PRIMARY PHOTOSYNTHESIS
    ARLT, T
    SCHMIDT, S
    KAISER, W
    LAUTERWASSER, C
    MEYER, M
    SCHEER, H
    ZINTH, W
    [J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1993, 90 (24) : 11757 - 11761
  • [6] INTRAMOLECULAR PHOTOINDUCED CHARGE SEPARATION AND CHARGE RECOMBINATION OF THE PRODUCT ION-PAIR STATES OF A SERIES OF FIXED-DISTANCE DYADS OF PORPHYRINS AND QUINONES - ENERGY-GAP AND TEMPERATURE DEPENDENCES OF THE RATE CONSTANTS
    ASAHI, T
    OHKOHCHI, M
    MATSUSAKA, R
    MATAGA, N
    ZHANG, RP
    OSUKA, A
    MARUYAMA, K
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (13) : 5665 - 5674
  • [7] ON THE MECHANISM OF THE PRIMARY CHARGE SEPARATION IN BACTERIAL PHOTOSYNTHESIS
    BIXON, M
    JORTNER, J
    MICHELBEYERLE, ME
    [J]. BIOCHIMICA ET BIOPHYSICA ACTA, 1991, 1056 (03) : 301 - 315
  • [8] MODEL REACTIONS IN PHOTOSYNTHESIS
    BOXER, SG
    [J]. BIOCHIMICA ET BIOPHYSICA ACTA, 1983, 726 (04) : 265 - 292
  • [9] CHARGE-TRANSFER ACROSS OBLIQUE BISPORPHYRINS - 2-CENTER PHOTOACTIVE MOLECULES
    BRUN, AM
    HARRIMAN, A
    HEITZ, V
    SAUVAGE, JP
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (23) : 8657 - 8663
  • [10] INITIAL ELECTRON-TRANSFER IN PHOTOSYNTHETIC REACTION CENTERS OF RHODOBACTER-CAPSULATUS MUTANTS
    CHAN, CK
    CHEN, LXQ
    DIMAGNO, TJ
    HANSON, DK
    NANCE, SL
    SCHIFFER, M
    NORRIS, JR
    FLEMING, GR
    [J]. CHEMICAL PHYSICS LETTERS, 1991, 176 (3-4) : 366 - 372