Identification of a triplet pair intermediate in singlet exciton fission in solution

被引：178

作者：

Stern, Hannah L. ^{[1
]}

Musser, Andrew J. ^{[1
]}

Gelinas, Simon ^{[1
]}

Parkinson, Patrick ^{[2
]}

Herz, Laura M. ^{[2
]}

Bruzek, Matthew J. ^{[3
]}

Anthony, John ^{[3
]}

Friend, Richard H. ^{[1
]}

Walker, Brian J. ^{[1
]}

机构：

[1] Univ Cambridge, Cavendish Lab, Cambridge CB3 0HE, England

[2] Univ Oxford, Clarendon Lab, Oxford OX1 3PU, England

[3] Univ Kentucky, Dept Chem, Lexington, KY 40506 USA

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2015年 / 112卷 / 25期

基金：

英国工程与自然科学研究理事会; 美国国家科学基金会;

关键词：

singlet fission; photochemistry; TIPS-tetracene; triplet; excimer; POLYCRYSTALLINE PENTACENE; CRYSTALLINE TETRACENE; SOLAR-CELLS; ENERGY; FLUORESCENCE; COHERENCES; GENERATION; DYNAMICS; KINETICS; EXCIMER;

D O I：

10.1073/pnas.1503471112

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：

Singlet exciton fission is the spin-conserving transformation of one spin-singlet exciton into two spin-triplet excitons. This exciton multiplication mechanism offers an attractive route to solar cells that circumvent the single-junction Shockley-Queisser limit. Most theoretical descriptions of singlet fission invoke an intermediate state of a pair of spin-triplet excitons coupled into an overall spin-singlet configuration, but such a state has never been optically observed. In solution, we show that the dynamics of fission are diffusion limited and enable the isolation of an intermediate species. In concentrated solutions of bis(triisopropylsilylethynyl)[TIPS]tetracene we find rapid (<100 ps) formation of excimers and a slower (similar to 10 ns) break up of the excimer to two triplet exciton-bearing free molecules. These excimers are spectroscopically distinct from singlet and triplet excitons, yet possess both singlet and triplet characteristics, enabling identification as a triplet pair state. We find that this triplet pair state is significantly stabilized relative to free triplet excitons, and that it plays a critical role in the efficient endothermic singlet fission process.

引用

页码：7656 / 7661

页数：6

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