Breaking the Bimolecular Crystal: The Effect of Side-Chain Length on Oligothiophene/Fullerene Intercalation

Edmund K. Burnett; Benjamin P. Cherniawski; Stephen J. Rosa; Detlef M. Smilgies; Sean Parkin; Alejandro L. Briseno

doi:10.1021/acs.chemmater.7b04702

Breaking the Bimolecular Crystal: The Effect of Side-Chain Length on Oligothiophene/Fullerene Intercalation

Edmund K. Burnett, Benjamin P. Cherniawski, Stephen J. Rosa, Detlef M. Smilgies, Sean Parkin, Alejandro L. Briseno

Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Polymer/fullerene bimolecular crystal formation has been investigated using a variety of conjugated polymers and fullerenes to understand the design rules that influence donor-acceptor interaction. Modifications of the polymer by varying the substitution side-chain position, density, and branching have demonstrated the importance of the "pocket" dimensions (free volume between side chains where the fullerene resides) for controlling intercalation. Yet the effect of pocket height has not been systematically explored because of the solubility limitations in polymers. In this report, we present an experimental investigation into the effect of the pocket height by synthesizing poly[2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene] dimers with varied side chain lengths and track the morphological changes of the dimer/fullerene blends using grazing-incidence X-ray scattering, thermal measurements, and photoluminescence quenching. We identify two regimes: (1) oligomers with side chains greater than or equal to heptyl (C7) form bimolecular crystals and (2) oligomers with less than or equal to hexyl (C6) form amorphous blends. This work provides the first observation of an order-to-disorder transition mediated by side-chain length in donor-fullerene intercalated blends.

Original language	English
Pages (from-to)	2550-2556
Number of pages	7
Journal	Chemistry of Materials
Volume	30
Issue number	8
DOIs	https://doi.org/10.1021/acs.chemmater.7b04702
State	Published - Apr 24 2018

Bibliographical note

Funding Information:
This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208.

Funding Information:
E.K.B., B.P.C., and A.L.B. acknowledge the support of the Office of Naval Research (N000141110636, N0001471410053). This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208.

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

Chemistry (all)
Chemical Engineering (all)
Materials Chemistry

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title = "Breaking the Bimolecular Crystal: The Effect of Side-Chain Length on Oligothiophene/Fullerene Intercalation",

abstract = "Polymer/fullerene bimolecular crystal formation has been investigated using a variety of conjugated polymers and fullerenes to understand the design rules that influence donor-acceptor interaction. Modifications of the polymer by varying the substitution side-chain position, density, and branching have demonstrated the importance of the {"}pocket{"} dimensions (free volume between side chains where the fullerene resides) for controlling intercalation. Yet the effect of pocket height has not been systematically explored because of the solubility limitations in polymers. In this report, we present an experimental investigation into the effect of the pocket height by synthesizing poly[2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene] dimers with varied side chain lengths and track the morphological changes of the dimer/fullerene blends using grazing-incidence X-ray scattering, thermal measurements, and photoluminescence quenching. We identify two regimes: (1) oligomers with side chains greater than or equal to heptyl (C7) form bimolecular crystals and (2) oligomers with less than or equal to hexyl (C6) form amorphous blends. This work provides the first observation of an order-to-disorder transition mediated by side-chain length in donor-fullerene intercalated blends.",

author = "Burnett, {Edmund K.} and Cherniawski, {Benjamin P.} and Rosa, {Stephen J.} and Smilgies, {Detlef M.} and Sean Parkin and Briseno, {Alejandro L.}",

note = "Funding Information: This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208. Funding Information: E.K.B., B.P.C., and A.L.B. acknowledge the support of the Office of Naval Research (N000141110636, N0001471410053). This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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AU - Smilgies, Detlef M.

AU - Parkin, Sean

AU - Briseno, Alejandro L.

N1 - Funding Information: This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208. Funding Information: E.K.B., B.P.C., and A.L.B. acknowledge the support of the Office of Naval Research (N000141110636, N0001471410053). This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208. Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/4/24

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Breaking the Bimolecular Crystal: The Effect of Side-Chain Length on Oligothiophene/Fullerene Intercalation

Abstract

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