GAUSSIAN FREE-ENERGY DEPENDENCE OF ELECTRON-TRANSFER RATES IN IRIDIUM COMPLEXES

被引：131

作者：

FOX, LS ^{[1
]}

KOZIK, M ^{[1
]}

WINKLER, JR ^{[1
]}

GRAY, HB ^{[1
]}

机构：

[1] BROOKHAVEN NATL LAB,DEPT CHEM,UPTON,NY 11973

来源：

SCIENCE | 1990年 / 247卷 / 4946期

关键词：

D O I：

10.1126/science.247.4946.1069

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The kinetics of photoinduced electron-transfer (ET) reactions have been measured in a series of synthetic donor-acceptor complexes. The electron donors are singlet or triplet excited iridium(I) dimers (Ir2), and the acceptors are N-alkylpyridinium groups covalently bound to phosphinite ligands on the Ir2 core. Rate constants for excited-state ET range from 3.5 × 106 to 1.1 × 1011 per second, and thermal back ET (pyridinium radical to Ir2+) rates vary from 2.0 × 1010 to 6.7 × 107 per second. The variation of these rates with driving force is in remarkably good agreement with the Marcus theory prediction of a Gaussian free-energy dependence.

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页码：1069 / 1071

页数：3

相关论文

共 35 条

[1] CALCULATION OF ELECTRON-TUNNELING MATRIX-ELEMENTS IN RIGID SYSTEMS - MIXED-VALENCE DITHIASPIROCYCLOBUTANE MOLECULES [J].

BERATAN, DN ;

HOPFIELD, JJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (06) :1584-1594

[2] LIMITING FORMS OF THE TUNNELING MATRIX ELEMENT IN THE LONG-DISTANCE BRIDGE MEDIATED ELECTRON-TRANSFER PROBLEM [J].

BERATAN, DN ;

ONUCHIC, JN ;

HOPFIELD, JJ .

JOURNAL OF CHEMICAL PHYSICS, 1985, 83 (10) :5325-5329

[3] ELECTRON-TUNNELING THROUGH RIGID MOLECULAR BRIDGES - BICYCLO[2.2.2]OCTANE [J].

BERATAN, DN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (15) :4321-4326

[4] THE ABSENCE OF A SPECTROSCOPICALLY RESOLVED INTERMEDIATE STATE P+B- IN BACTERIAL PHOTOSYNTHESIS [J].

BRETON, J ;

MARTIN, JL ;

PETRICH, J ;

MIGUS, A ;

ANTONETTI, A .

FEBS LETTERS, 1986, 209 (01) :37-43

[5] FEMTOSECOND SPECTROSCOPY OF EXCITATION-ENERGY TRANSFER AND INITIAL CHARGE SEPARATION IN THE REACTION CENTER OF THE PHOTOSYNTHETIC BACTERIUM RHODOPSEUDOMONAS-VIRIDIS [J].

BRETON, J ;

MARTIN, JL ;

MIGUS, A ;

ANTONETTI, A ;

ORSZAG, A .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1986, 83 (14) :5121-5125

[6]

BROST RD, UNPUB

[7] SOLVENT REORGANIZATION IN OPTICAL AND THERMAL ELECTRON-TRANSFER PROCESSES [J].

BRUNSCHWIG, BS ;

EHRENSON, S ;

SUTIN, N .

JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (16) :3657-3668

[8] PHOTOCHEMISTRY OF RU(BPY)32+ - SOLVENT EFFECTS [J].

CASPAR, JV ;

MEYER, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (17) :5583-5590

[9] INTRAMOLECULAR LONG-DISTANCE ELECTRON-TRANSFER IN ORGANIC-MOLECULES [J].

CLOSS, GL ;

MILLER, JR .

SCIENCE, 1988, 240 (4851) :440-447

[10] DISTANCE, STEREOELECTRONIC EFFECTS, AND THE MARCUS INVERTED REGION IN INTRAMOLECULAR ELECTRON-TRANSFER IN ORGANIC RADICAL-ANIONS [J].

CLOSS, GL ;

CALCATERRA, LT ;

GREEN, NJ ;

PENFIELD, KW ;

MILLER, JR .

JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (16) :3673-3683

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