Temperature and isotope effects on the rates of photoinduced iridium(I)-pyridinium electron-transfer reactions

被引：7

作者：

Wiedenfeld, D ^{[1
]}

Bachrach, M ^{[1
]}

McCleskey, TM ^{[1
]}

Hill, MG ^{[1
]}

Gray, HB ^{[1
]}

Winkler, JR ^{[1
]}

机构：

[1] CALTECH,BECKMAN INST,PASADENA,CA 91125

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 1997年 / 101卷 / 44期

关键词：

D O I：

10.1021/jp963984g

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：

Intramolecular electron-transfer (ET) rates have been measured as functions of reaction driving force (0.0-2.0 eV) and temperature (200-280 K) for a series of iridium dimers (Ir-2) covalently bound to substituted pyridinium (py(+)) groups. We found that the rates of recombination reactions (py(.) --> Ir-2(+)) at high driving forces are strongly dependent on temperature and that Ir-2* --> py(+) and py(.) --> Ir-2(+) rates in both the normal and inverted regions are slower on deuteration of the pyridinium accepters. Analysis of the rates in terms of semiclassical theory gives the following parameter values: H-AB = 52(9) cm(-1), lambda = 1.05(2) eV (280 K); H-AB = 22(2) cm(-1), lambda = 1.04(1) eV (210 K). 4-Phenyl-N-ethylpyridinium iodide, chosen as a model for the accepters in the Ir-2* --> py(+) reactions, exhibited resonance Raman scattering that implicated a 1565-cm(-1) mode as dominant for inner-sphere reorganization.

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页码：8823 / 8826

页数：4

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共 22 条

[11] ELECTRON-TRANSFER REACTIONS IN THE MARCUS INVERTED REGION - DIFFERENCES IN SOLVATION AND ELECTRONIC COUPLING BETWEEN EXCITED CHARGE-TRANSFER COMPLEXES AND GEMINATE RADICAL ION-PAIRS [J].

GOULD, IR ;

MOODY, R ;

FARID, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (21) :7242-7244

[12] SPECIFIC DEUTERIUM-ISOTOPE EFFECTS ON THE RATES OF ELECTRON-TRANSFER WITHIN GEMINATE RADICAL-ION PAIRS [J].

GOULD, IR ;

FARID, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (23) :7883-7885

[13] RETURN ELECTRON-TRANSFER WITHIN GEMINATE RADICAL ION-PAIRS - OBSERVATION OF THE MARCUS INVERTED REGION [J].

GOULD, IR ;

EGE, D ;

MATTES, SL ;

FARID, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (12) :3794-3796

[14] ELECTRON-TRANSFER REACTIONS IN THE MARCUS INVERTED REGION - CHARGE RECOMBINATION VERSUS CHARGE SHIFT REACTIONS [J].

GOULD, IR ;

MOSER, JE ;

ARMITAGE, B ;

FARID, S ;

GOODMAN, JL ;

HERMAN, MS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (05) :1917-1919

[15] PEPTIDE-MEDIATED INTRAMOLECULAR ELECTRON-TRANSFER - LONG-RANGE DISTANCE DEPENDENCE [J].

ISIED, SS ;

OGAWA, MY ;

WISHART, JF .

CHEMICAL REVIEWS, 1992, 92 (03) :381-394

[16] TEMPERATURE EFFECTS ON INTRAMOLECULAR ELECTRON-TRANSFER KINETICS UNDER NORMAL, INVERTED, AND NEARLY OPTIMAL CONDITIONS [J].

KROON, J ;

OEVERING, H ;

VERHOEVEN, JW ;

WARMAN, JM ;

OLIVER, AM ;

PADDONROW, MN .

JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (19) :5065-5069

[17] Structural fluctuations, spin, reorganization energy, and tunneling energy control of intramolecular electron transfer: The surprising case of electron transfer in a d(8)-d(8) bimetallic system [J].

Kurnikov, IV ;

Zusman, LD ;

Kurnikova, MG ;

Farid, RS ;

Beratan, DN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (24) :5690-5700

[18] TEMPERATURE-INDEPENDENT LONG-RANGE ELECTRON-TRANSFER REACTIONS IN THE MARCUS INVERTED REGION [J].

LIANG, N ;

MILLER, JR ;

CLOSS, GL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (13) :5353-5354

[19] THE EXCITED-STATE POTENTIAL-ENERGY SURFACE FOR THE PHOTOISOMERIZATION OF TETRAPHENYLETHYLENE - A FLUORESCENCE AND PICOSECOND OPTICAL CALORIMETRY INVESTIGATION [J].

MA, JS ;

DUTT, GB ;

WALDECK, DH ;

ZIMMT, MB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (23) :10619-10629

[20] ELECTRON TRANSFERS IN CHEMISTRY AND BIOLOGY [J].

MARCUS, RA ;

SUTIN, N .

BIOCHIMICA ET BIOPHYSICA ACTA, 1985, 811 (03) :265-322