Theory-Driven Insight into the Crystal Packing of Trialkylsilylethynyl Pentacenes

Karl J. Thorley, Tristan W. Finn, Karol Jarolimek, John E. Anthony, Chad Risko

Research output: Contribution to journalArticlepeer-review

30 Scopus citations


The functionalization of oligoacenes and similar π-conjugated chromophores with trialkylsilylethynyl groups has proven to be a versatile means to enhance solubility and solution processability and engineer solid-state packing arrangements to produce organic semiconductors that demonstrate outstanding charge-carrier transport characteristics. While a general, empirical-based geometric model has been developed and implemented to direct the solid-state packing arrangements of these molecular materials, there exist numerous examples where the model falters. Here, we employ electronic structure methods to probe the noncovalent, intermolecular interactions of two closely related systems that result in two very different crystal packing configurations: triisopropylsilylethynyl (TIPS) pentacene and its triethylsilylethynyl (TES) analog. The quantum-chemical evaluation details how the slightly larger electron density contained within the volume of the TIPS moiety with respect to TES is in part responsible for the solid-state packing variations. We also make use of periodic density functional theory (DFT) methods to develop in silico polymorphs of these systems and explore the electronic characteristics of varied packing arrangements. The results suggest that TES pentacene, if processed correctly, could be developed into a material with improved charge-carrier transport characteristics when compared to its native form. Overall, the theory-driven insight developed in this work lays an important foundation to build a more robust crystal engineering paradigm for these technologically relevant organic semiconductors.

Original languageEnglish
Pages (from-to)2502-2512
Number of pages11
JournalChemistry of Materials
Issue number6
StatePublished - Mar 28 2017

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry


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