Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission

Wang, Xiaopeng; Liu, Xingyu; Tom, Rithwik; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

doi:10.1021/acs.jpcc.8b12549

Title: Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission

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Abstract

Singlet fission (SF), a spin-conserving process where one singlet exciton is converted into two triplet excitons, may improve the efficiency of organic photovoltaics. Only a few materials have been experimentally observed to undergo intermolecular SF, most of which are acenes and their derivatives. Using many-body perturbation theory in the GW approximation and the Bethe–Salpeter equation, we systematically investigate the electronic and excitonic properties of tetracene, pentacene, and their phenylated derivatives in the gas phase and solid state. Their potential for SF is evaluated with respect to the thermodynamic driving force and the singlet exciton charge-transfer character. In both the gas phase and solid state, pentacene and its derivatives are more promising than tetracene analogues. Within a family of molecules containing the same acene backbone, increasing the number of phenyl side groups is detrimental for the SF driving force in the gas phase. However, in the solid state, the SF driving force and the exciton character are modulated by intermolecular interactions present within different packing arrangements. Molecules with a higher number of phenyl side groups often form crystals with less cofacial interactions between the acene backbones. These crystals are found to exhibit a higher SF driving force and a higher degreemore »« less

Authors:

Wang, Xiaopeng ^[1]; Liu, Xingyu ^[1]; Tom, Rithwik ^[1]; Cook, Cameron ^[2];

^[2];

^[1]

Carnegie Mellon Univ., Pittsburgh, PA (United States)
California State Polytechnic Univ., Pomona, CA (United States)

Publication Date:: Mon Feb 18 00:00:00 EST 2019

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1530410

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 10; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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                    Wang, Xiaopeng, Liu, Xingyu, Tom, Rithwik, Cook, Cameron, Schatschneider, Bohdan, and Marom, Noa. Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpcc.8b12549.

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                    Wang, Xiaopeng, Liu, Xingyu, Tom, Rithwik, Cook, Cameron, Schatschneider, Bohdan, & Marom, Noa. Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission.  United States.  https://doi.org/10.1021/acs.jpcc.8b12549

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                    Wang, Xiaopeng, Liu, Xingyu, Tom, Rithwik, Cook, Cameron, Schatschneider, Bohdan, and Marom, Noa. Mon .  
"Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission".  United States.  https://doi.org/10.1021/acs.jpcc.8b12549.  https://www.osti.gov/servlets/purl/1530410.

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@article{osti_1530410,

  title        = {Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission},

  author       = {Wang, Xiaopeng and Liu, Xingyu and Tom, Rithwik and Cook, Cameron and Schatschneider, Bohdan and Marom, Noa},

  abstractNote = {Singlet fission (SF), a spin-conserving process where one singlet exciton is converted into two triplet excitons, may improve the efficiency of organic photovoltaics. Only a few materials have been experimentally observed to undergo intermolecular SF, most of which are acenes and their derivatives. Using many-body perturbation theory in the GW approximation and the Bethe–Salpeter equation, we systematically investigate the electronic and excitonic properties of tetracene, pentacene, and their phenylated derivatives in the gas phase and solid state. Their potential for SF is evaluated with respect to the thermodynamic driving force and the singlet exciton charge-transfer character. In both the gas phase and solid state, pentacene and its derivatives are more promising than tetracene analogues. Within a family of molecules containing the same acene backbone, increasing the number of phenyl side groups is detrimental for the SF driving force in the gas phase. However, in the solid state, the SF driving force and the exciton character are modulated by intermolecular interactions present within different packing arrangements. Molecules with a higher number of phenyl side groups often form crystals with less cofacial interactions between the acene backbones. These crystals are found to exhibit a higher SF driving force and a higher degree of singlet exciton charge-transfer character. Finally in particular, 5,7,12,14-tetraphenylpentacene, 1,4,6,8,11,13-hexaphenylpentacene, and 1,2,3,4,6,8,9,10,11,13-decaphenylpentacene emerge as promising candidates for intermolecular SF in the solid state.},

  doi          = {10.1021/acs.jpcc.8b12549},

  journal      = {Journal of Physical Chemistry. C},

  number       = 10,

  volume       = 123,

  place        = {United States},

  year         = {Mon Feb 18 00:00:00 EST 2019},

  month        = {Mon Feb 18 00:00:00 EST 2019}

}

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