Linear free-energy relationship for electron-transfer processes of pyrrolidinofullerenes with tetrakis(dimethylamino)ethylene in ground and excited states

被引:27
作者
Luo, CP [1 ]
Fujitsuka, M
Huang, CH
Ito, O
机构
[1] Tohoku Univ, Inst Chem React Sci, Aoba Ku, Sendai, Miyagi 9808577, Japan
[2] Peking Univ, State Key Lab Rare Earth Mat Chem & Applicat, Beijing 100871, Peoples R China
关键词
D O I
10.1039/a901837i
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
Systematic studies of electron-transfer processes in the ground states and excited triplet states of pyrrolidinofullerenes {C-60(C3H6N)R [R = H (1), p-C6H4NO2 (2), p-C6H4CHO (3), p-C6H5 (4), p-C6H4OMe (5), p-C6H4NMe2 (6)]} with tetrakis(dimethylamino)ethylene (TDAE) have been carried out by steady-state and transient absorption measurements in the visible-NIR region. Analyses of the equilibria of the electron-transfer processes in the ground states indicate that free ion radicals are produced in polar solvents. Photoinduced electron-transfer processes via (T)(C-60(C3H6N)R)* were observed by applying a perturbation to the equilibria of the electron-transfer reactions in the ground states by laser flash photolysis. Based on the relationship of the thermodynamic data and kinetic data, the electron-transfer rate constants in the ground states (k(et)(G)) can be evaluated. The k(et)(G) values are affected by the substituents to a smaller extent compared with the equilibrium constants (K) in polar solvents; alpha = 0.6 in Delta log k(et)(G) = alpha Delta log K. This alpha value indicates that the activation energies of forward electron transfer in the ground states vary moderately with the thermodynamic stabilities of (C-60(C3H6N)R)(.-). Electron-transfer rate constants via (T)(C-60(C3H6N)R)*, which are close to the diffusion-controlled limit, do not show a large substituent effect (alpha' = 0), because of their highly exothermic processes. Such a linear free-energy relationship can be extended to other systems such as (T)(C-60(C3H6N)R)*/N,N-dimethylaniline, from which valuable information for electron-transfer processes can be obtained.
引用
收藏
页码:2923 / 2928
页数:6
相关论文
共 56 条
  • [31] Photoinduced charge separation and charge recombination to a triplet state in a carotene-porphyrin-fullerene triad
    Liddell, PA
    Kuciauskas, D
    Sumida, JP
    Nash, B
    Nguyen, D
    Moore, AL
    Moore, TA
    Gust, D
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (06) : 1400 - 1405
  • [32] Substituent and solvent effects on photoexcited states of functionalized fullerene[60]
    Luo, C
    Fujitsuka, M
    Watanabe, A
    Ito, O
    Gan, LB
    Huang, Y
    Huang, CH
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1998, 94 (04): : 527 - 532
  • [33] Investigation of the photoelectrochemistry of C-60 and its pyrrolidine derivatives by monolayer-modified SnO2 electrodes
    Luo, CP
    Huang, CH
    Gan, LB
    Zhou, DJ
    Xia, WS
    Zhuang, QK
    Zhao, YL
    Huang, YY
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (41) : 16685 - 16689
  • [34] Photoinduced electron transfer from N,N-dimethylaniline to pyrrolidinofullerenes (C60(C3H6N)R):: Emphasized substituent effects with solvent polarity change
    Luo, CP
    Fujitsuka, M
    Huang, CH
    Ito, O
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (45) : 8716 - 8721
  • [35] Quantitative spectroscopic studies of the photoexcited state properties of methano- and pyrrolidino-[60]fullerene derivatives
    Ma, B
    Bunker, CE
    Guduru, R
    Zhang, XF
    Sun, YP
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (31) : 5626 - 5632
  • [36] C60-based electroactive organofullerenes
    Martin, N
    Sanchez, L
    Illescas, B
    Perez, I
    [J]. CHEMICAL REVIEWS, 1998, 98 (07) : 2527 - 2547
  • [37] PREPARATION AND ISOLATION OF 3 ISOMERIC C-70 ISOXAZOLINES - STRONG DESHIELDING IN THE POLAR-REGION OF C-70
    MEIER, MS
    POPLAWSKA, M
    COMPTON, AL
    SHAW, JP
    SELEGUE, JP
    GUARR, TF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (16) : 7044 - 7048
  • [38] NIERENGARTEN JN, 1997, HELV CHIM ACTA, V82, P2238
  • [39] Photophysical properties of C-60(C6H5)(5)Cl: A laser flash photolysis and pulse radiolysis study
    Palit, DK
    Mohan, H
    Birkett, PR
    Mittal, JP
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (30) : 5418 - 5422
  • [40] EXPERIMENTAL-EVIDENCE FOR SEGREGATED RING CURRENTS IN C-60
    PRATO, M
    SUZUKI, T
    WUDL, F
    LUCCHINI, V
    MAGGINI, M
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (17) : 7876 - 7877