Triplet Separation Drives Singlet Fission after Femtosecond Correlated Triplet Pair Production in Rubrene

被引:118
作者
Breen, Ilana [1 ]
Tempelaar, Roel [2 ]
Bizimana, Laurie A. [1 ]
Kloss, Benedikt [2 ]
Reichman, David R. [2 ]
Turner, Daniel B. [1 ]
机构
[1] NYU, Dept Chem, 100 Washington Sq East, New York, NY 10003 USA
[2] Columbia Univ, Dept Chem, 3000 Broadway, New York, NY 10027 USA
基金
美国国家科学基金会;
关键词
EXCITON-FISSION; ELECTRONIC SPECTROSCOPY; ORGANIC SEMICONDUCTORS; TRANSPORT-PROPERTIES; ULTRAFAST DYNAMICS; AMORPHOUS RUBRENE; CHARGE-TRANSPORT; SOLAR-CELLS; THIN-FILM; CRYSTALS;
D O I
10.1021/jacs.7b02621
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Singlet fission, a multistep molecular process in which one photon generates two triplet excitons, holds great technological promise. Here, by applying a combination of transient transmittance and two-dimensional electronic spectroscopy with 5 fs laser pulses, we resolve the full set of fission steps before the onset of spin dephasing. In addition to its role as a viable singlet fission material, single-crystalline rubrene is selected because its energetics and transition dipole alignment uniquely allow for the unambiguous identification of the various fission steps through their contributions to distinct spectroscopic features. The measurements reveal that the neighboring correlated triplet pair achieves its maximum population within 20 fs. Subsequent growth of the triplet signal on picosecond time scales is attributable to spatial separation of the triplets, proceeding nonadiabatically through weakly coupled but near-resonant states. As such, we provide evidence in crystalline rubrene for a singlet fission step that, until now, has not been convincingly observed.
引用
收藏
页码:11745 / 11751
页数:7
相关论文
共 50 条
[41]   Recent advances in triplet-triplet annihilation upconversion and singlet fission, towards solar energy applications [J].
Carrod, Andrew J. ;
Gray, Victor ;
Boerjesson, Karl .
ENERGY & ENVIRONMENTAL SCIENCE, 2022, 15 (12) :4982-5016
[42]   Benchmarking singlet and triplet excitation energies of molecular semiconductors for singlet fission: Tuning the amount of HF exchange and adjusting local correlation to obtain accurate functionals for singlet-triplet gaps [J].
Brueckner, Charlotte ;
Engels, Bernd .
CHEMICAL PHYSICS, 2017, 482 :319-338
[43]   Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene [J].
Monahan, Nicholas R. ;
Sun, Dezheng ;
Tamura, Hiroyuki ;
Williams, KristopherW. ;
Xu, Bolei ;
Zhong, Yu ;
Kumar, Bharat ;
Nuckolls, Colin ;
Harutyunyan, Avetik R. ;
Chen, Gugang ;
Dai, Hai-Lung ;
Beljonne, David ;
Rao, Yi ;
Zhu, X. -Y. .
NATURE CHEMISTRY, 2017, 9 (04) :341-346
[44]   Soluble Diphenylhexatriene Dimers for Intramolecular Singlet Fission with High Triplet Energy [J].
Millington, Oliver ;
Montanaro, Stephanie ;
Leventis, Anastasia ;
Sharma, Ashish ;
Dowland, Simon A. ;
Sawhney, Nipun ;
Fallon, Kealan J. ;
Zeng, Weixuan ;
Congrave, Daniel G. ;
Musser, Andrew J. ;
Rao, Akshay ;
Bronstein, Hugo .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2023, 145 (04) :2499-2510
[45]   Harnessing Molecular Vibrations to Probe Triplet Dynamics During Singlet Fission [J].
Grieco, Christopher ;
Kennehan, Eric R. ;
Rimshaw, Adam ;
Payne, Marcia M. ;
Anthony, John E. ;
Asbury, John B. .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2017, 8 (23) :5700-5706
[46]   Triplet diffusion in singlet exciton fission sensitized pentacene solar cells [J].
Tabachnyk, Maxim ;
Ehrler, Bruno ;
Bayliss, Sam ;
Friend, Richard H. ;
Greenham, Neil C. .
APPLIED PHYSICS LETTERS, 2013, 103 (15)
[47]   Promoting multiexciton interactions in singlet fission and triplet fusion upconversion dendrimers [J].
He, Guiying ;
Churchill, Emily M. ;
Parenti, Kaia R. ;
Zhang, Jocelyn ;
Narayanan, Pournima ;
Namata, Faridah ;
Malkoch, Michael ;
Congreve, Daniel N. ;
Cacciuto, Angelo ;
Sfeir, Matthew Y. ;
Campos, Luis M. .
NATURE COMMUNICATIONS, 2023, 14 (01)
[48]   Temperature-Dependent Recombination of Triplet Biexcitons in Singlet Fission of Hexacene [J].
Qian, Yuqin ;
Huang-Fu, Zhi-Chao ;
Zhang, Tong ;
Li, Xia ;
Harutyunyan, Avetik R. ;
Chen, Gugang ;
Chen, Hanning ;
Rao, Yi .
JOURNAL OF PHYSICAL CHEMISTRY C, 2022, 126 (19) :8377-8383
[49]   Nanostructured Singlet Fission Photovoltaics Subject to Triplet-Charge Annihilation [J].
Thompson, Nicholas J. ;
Hontz, Eric ;
Congreve, Daniel N. ;
Bahlke, Matthias E. ;
Reineke, Sebastian ;
Van Voorhis, Troy ;
Baldo, Marc A. .
ADVANCED MATERIALS, 2014, 26 (09) :1366-1371
[50]   Distinguishing between Triplet-Pair State and Excimer Emission in Singlet Fission Chromophores Using Mixed Thin Films [J].
Hausch, Julian ;
Berges, Adam J. ;
Zeiser, Clemens ;
Rammler, Tim ;
Morlok, Arne ;
Bredehoft, Jona ;
Hammer, Sebastian ;
Pflaum, Jens ;
Bardeen, Christopher J. ;
Broch, Katharina .
JOURNAL OF PHYSICAL CHEMISTRY C, 2022, 126 (15) :6686-6693