Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung; Nuckolls, Colin; Loo, Yueh -Lin

doi:10.1021/acs.chemmater.7b00627

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

Journal Article · Tue Apr 25 00:00:00 EDT 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b00627· OSTI ID:1399740

Hiszpanski, Anna M. ^[1]; Woll, Arthur R. ^[2]; Kim, Bumjung ^[3]; ^[4]; ^[5]

Princeton Univ., Princeton, NJ (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Cornell Univ., Ithaca, NY (United States)
Columbia Univ., New York, NY (United States); New Jersey City Univ., Jersey City, NJ (United States)
Columbia Univ., New York, NY (United States)
Princeton Univ., Princeton, NJ (United States)

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior of contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2₁/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1399740

Report Number(s):: LLNL-JRNL--713258

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 10 Vol. 29; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Fluorination‐Induced Evolution of Columnar Packing in Fluorous Triphenylenes and Benzotriphenylenes Rippy, Kerry C.; DeWeerd, Nicholas J.; Kuvychko, Igor V. ChemPlusChem, Vol. 83, Issue 12 https://doi.org/10.1002/cplu.201800451	journal	October 2018
Fluorination‐Induced Evolution of Columnar Packing in Fluorous Triphenylenes and Benzotriphenylenes Rippy, Kerry C.; DeWeerd, Nicholas J.; Kuvychko, Igor V. ChemPlusChem, Vol. 83, Issue 12 https://doi.org/10.1002/cplu.201800572	journal	October 2018
Computationally aided design of a high-performance organic semiconductor: the development of a universal crystal engineering core Petty, Anthony J.; Ai, Qianxiang; Sorli, Jeni C. Chemical Science, Vol. 10, Issue 45 https://doi.org/10.1039/c9sc02930c	journal	January 2019
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Polymorphism of terthio-phene with surface confinement. Resel, Roland; Jones, Andrew OF; Schweicher, Guillaume International Union of Crystallography (IUCr) https://doi.org/10.17863/cam.26939	journalarticle	January 2018

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