A Design Strategy for Intramolecular Singlet Fission Mediated by Charge-transfer States In donor-acceptor Organic Materials

Overview

Journal Nat Mater

Date 2015 Jan 13

PMID 25581625

Citations 49

Authors

Erik Busby

Jianlong Xia

Qin Wu

Jonathan Z Low

Rui Song

John R Miller

X-Y Zhu

Luis M Campos

Matthew Y Sfeir

Affiliations

Soon will be listed here.

Abstract

The ability to advance our understanding of multiple exciton generation (MEG) in organic materials has been restricted by the limited number of materials capable of singlet fission. A particular challenge is the development of materials that undergo efficient intramolecular fission, such that local order and strong nearest-neighbour coupling is no longer a design constraint. Here we address these challenges by demonstrating that strong intrachain donor-acceptor interactions are a key design feature for organic materials capable of intramolecular singlet fission. By conjugating strong-acceptor and strong-donor building blocks, small molecules and polymers with charge-transfer states that mediate population transfer between singlet excitons and triplet excitons are synthesized. Using transient optical techniques, we show that triplet populations can be generated with yields up to 170%. These guidelines are widely applicable to similar families of polymers and small molecules, and can lead to the development of new fission-capable materials with tunable electronic structure, as well as a deeper fundamental understanding of MEG.

Citing Articles

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Intra- and Intermolecular Charge-Transfer Dynamics of Carbene-Metal-Amide Photosensitizers.

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Catalyzing Singlet Fission by Transition Metals: Second versus Third Row Effects.

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A Nonorthogonal Configuration Interaction Approach to Singlet Fission in Perylenediimide Compounds.

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Non-orthogonal Configuration Interaction Study on the Effect of Thermal Distortions on the Singlet Fission Process in Photoexcited Pure and B,N-Doped Pentacene Crystals.

Lopez X, Straatsma T, Sanchez-Mansilla A, de Graaf C J Phys Chem C Nanomater Interfaces. 2023; 127(33):16249-16258.

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References

Chan W, Berkelbach T, Provorse M, Monahan N, Tritsch J, Hybertsen M . The quantum coherent mechanism for singlet fission: experiment and theory. Acc Chem Res. 2013; 46(6):1321-9. DOI: 10.1021/ar300286s. View

Guo J, Ohkita H, Benten H, Ito S . Near-IR femtosecond transient absorption spectroscopy of ultrafast polaron and triplet exciton formation in polythiophene films with different regioregularities. J Am Chem Soc. 2009; 131(46):16869-80. DOI: 10.1021/ja906621a. View

Musser A, Al-Hashimi M, Maiuri M, Brida D, Heeney M, Cerullo G . Activated singlet exciton fission in a semiconducting polymer. J Am Chem Soc. 2013; 135(34):12747-54. DOI: 10.1021/ja405427j. View

Berkelbach T, Hybertsen M, Reichman D . Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange. J Chem Phys. 2013; 138(11):114103. DOI: 10.1063/1.4794427. View

Berkelbach T, Hybertsen M, Reichman D . Microscopic theory of singlet exciton fission. I. General formulation. J Chem Phys. 2013; 138(11):114102. DOI: 10.1063/1.4794425. View

Gradinaru C, Kennis J, Papagiannakis E, van Stokkum I, Cogdell R, Fleming G . An unusual pathway of excitation energy deactivation in carotenoids: singlet-to-triplet conversion on an ultrafast timescale in a photosynthetic antenna. Proc Natl Acad Sci U S A. 2001; 98(5):2364-9. PMC: 30144. DOI: 10.1073/pnas.051501298. View

Yost S, Lee J, Wilson M, Wu T, McMahon D, Parkhurst R . A transferable model for singlet-fission kinetics. Nat Chem. 2014; 6(6):492-7. DOI: 10.1038/nchem.1945. View

Tritsch J, Chan W, Wu X, Monahan N, Zhu X . Harvesting singlet fission for solar energy conversion via triplet energy transfer. Nat Commun. 2013; 4:2679. DOI: 10.1038/ncomms3679. View

van Stokkum I, Larsen D, van Grondelle R . Global and target analysis of time-resolved spectra. Biochim Biophys Acta. 2004; 1657(2-3):82-104. DOI: 10.1016/j.bbabio.2004.04.011. View

10.

You J, Dou L, Yoshimura K, Kato T, Ohya K, Moriarty T . A polymer tandem solar cell with 10.6% power conversion efficiency. Nat Commun. 2013; 4:1446. PMC: 3660643. DOI: 10.1038/ncomms2411. View

11.

Chan W, Ligges M, Zhu X . The energy barrier in singlet fission can be overcome through coherent coupling and entropic gain. Nat Chem. 2012; 4(10):840-5. DOI: 10.1038/nchem.1436. View

12.

Gelinas S, Rao A, Kumar A, Smith S, Chin A, Clark J . Ultrafast long-range charge separation in organic semiconductor photovoltaic diodes. Science. 2013; 343(6170):512-6. DOI: 10.1126/science.1246249. View

13.

Chan W, Ligges M, Jailaubekov A, Kaake L, Miaja-Avila L, Zhu X . Observing the multiexciton state in singlet fission and ensuing ultrafast multielectron transfer. Science. 2011; 334(6062):1541-5. DOI: 10.1126/science.1213986. View

14.

Oliva M, Casado J, Lopez Navarrete J, Patchkovskii S, Goodson 3rd T, Harpham M . Do [all]-S,S'-dioxide oligothiophenes show electronic and optical properties of oligoenes and/or of oligothiophenes?. J Am Chem Soc. 2010; 132(17):6231-42. DOI: 10.1021/ja101015q. View

15.

Sun Y, Welch G, Leong W, Takacs C, Bazan G, Heeger A . Solution-processed small-molecule solar cells with 6.7% efficiency. Nat Mater. 2011; 11(1):44-8. DOI: 10.1038/nmat3160. View

16.

Beljonne D, Yamagata H, Bredas J, Spano F, Olivier Y . Charge-transfer excitations steer the Davydov splitting and mediate singlet exciton fission in pentacene. Phys Rev Lett. 2013; 110(22):226402. DOI: 10.1103/PhysRevLett.110.226402. View

17.

Ehrler B, Walker B, Bohm M, Wilson M, Vaynzof Y, Friend R . In situ measurement of exciton energy in hybrid singlet-fission solar cells. Nat Commun. 2012; 3:1019. DOI: 10.1038/ncomms2012. View

18.

Smith M, Michl J . Singlet fission. Chem Rev. 2010; 110(11):6891-936. DOI: 10.1021/cr1002613. View

19.

Wei S, Xia J, Dell E, Jiang Y, Song R, Lee H . Bandgap engineering through controlled oxidation of polythiophenes. Angew Chem Int Ed Engl. 2014; 53(7):1832-6. DOI: 10.1002/anie.201309398. View

20.

Bredas J, Norton J, Cornil J, Coropceanu V . Molecular understanding of organic solar cells: the challenges. Acc Chem Res. 2009; 42(11):1691-9. DOI: 10.1021/ar900099h. View