Even-Odd Alkyl Chain-Length Alternation Regulates Oligothiophene Crystal Structure

Edmund K. Burnett, Qianxiang Ai, Benjamin P. Cherniawski, Sean R. Parkin, Chad Risko, Alejandro L. Briseno

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20 Scopus citations


Alkyl chains of varied length and steric bulk are generally appended to π-conjugated chromophores to increase solubility. These alkyl chains also regulate many aspects of the solid-state packing and, in turn, resultant electronic and optical properties of organic semiconductors, yet there remains little understanding as to how these moieties govern such characteristics. Here, we report on a series of (2,5-bis(3-alkylthiophen-2-yl) thieno[3,2-b]thiophenes) (BTTT) monomers where the single-crystal packing configurations and melting points alternate as a function of whether the alkyl side chains have an even or odd number of carbon atoms. When the alkyl chains contain an even number of carbon atoms, the molecules predominantly crystallize with the BTTT units of the stacked lamellae aligned in the same direction. In contrast, when the number of carbon atoms is odd, alternating lamellae are twisted with respect to their neighbors, i.e. the BTTT moieties in one layer are aligned in an orthogonal-like fashion to those in its neighboring lamellae, and the crystal melting points tend to be higher than those with the even-numbered alkyl chains. With density functional theory calculations and geometric analyses, the variations in crystal structure and thus the differences in physical properties are rationalized by an oscillating interlayer interaction that is a function of alkyl side chain atom count and length. This study characterizes an extreme case of an organic semiconductor crystal packing alternation to highlight the effect of even-odd assembly as an underutilized and under-reported handle for tuning the molecular packing of organic semiconductor materials.

Original languageEnglish
Pages (from-to)6900-6907
Number of pages8
JournalChemistry of Materials
Issue number17
StatePublished - Sep 10 2019

Bibliographical note

Funding Information:
E.K.B, B.P.C, and A.L.B acknowledge the Office of Naval Research (Grants N000141110636 and N0001471410053). C.R. and Q.A. acknowledge the National Science Foundation (Award DMR-1627428) for support of this work. Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS). Crystallography at UK was supported by the NSF (Awards MRI CHE-0319176 and CHE-1625732). We thank Dr. Kevin Gagnon at the ALS, and access to the Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under Contract DE-AC02-05CH11231.

Publisher Copyright:
© 2019 American Chemical Society.

ASJC Scopus subject areas

  • Chemistry (all)
  • Chemical Engineering (all)
  • Materials Chemistry


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