Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing
Abstract
Small molecules (SMs) with unique optical or electronic properties provide an opportunity to incorporate functionality into block copolymer (BCP)-based supramolecules. However, the assembly of supramolecules based on these highly crystalline molecules differs from their less crystalline counterparts. In this work, two families of organic semiconductor SMs are investigated, where the composition of the crystalline core, the location (side- vs end-functionalization) of the alkyl solubilizing groups, and the constitution (branched vs linear) of the alkyl groups are varied. With these SMs, we present a systematic study of how the phase behavior of the SMs affects the overall assembly of these organic semiconductor-based supramolecules. The incorporation of SMs has a large effect on the interfacial curvature, the supramolecular periodicity, and the overall supramolecular morphology. The crystal packing of the SM within the supramolecule does not necessarily lead to the assembly of the comb block within the BCP microdomains, as is normally observed for alkyl-containing supramolecules. An unusual lamellar morphology with a wavy interface between the microdomains is observed due to changes in the packing structure of the small molecule within BCP microdomains. Since the supramolecular approach is modular and small molecules can be readily switched out, present studies provide useful guidance towardmore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Ewha Womans Univ., Seoul (Korea)
- Univ. of California, Berkeley, CA (United States); King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1240182
- Grant/Contract Number:
- AC02-05CH11231; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 49; Journal Issue: 3; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 36 MATERIALS SCIENCE; Morphology; Supramolecular structures and assemblies; Crystallization; Crystal structure; Transmission electron microscopy
Citation Formats
Rancatore, Benjamin J., Kim, BongSoo, Mauldin, Clayton E., Fréchet, Jean J., and Xu, Ting. Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing. United States: N. p., 2016.
Web. doi:10.1021/acs.macromol.5b02449.
Rancatore, Benjamin J., Kim, BongSoo, Mauldin, Clayton E., Fréchet, Jean J., & Xu, Ting. Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing. United States. https://doi.org/10.1021/acs.macromol.5b02449
Rancatore, Benjamin J., Kim, BongSoo, Mauldin, Clayton E., Fréchet, Jean J., and Xu, Ting. Thu .
"Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing". United States. https://doi.org/10.1021/acs.macromol.5b02449. https://www.osti.gov/servlets/purl/1240182.
@article{osti_1240182,
title = {Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing},
author = {Rancatore, Benjamin J. and Kim, BongSoo and Mauldin, Clayton E. and Fréchet, Jean J. and Xu, Ting},
abstractNote = {Small molecules (SMs) with unique optical or electronic properties provide an opportunity to incorporate functionality into block copolymer (BCP)-based supramolecules. However, the assembly of supramolecules based on these highly crystalline molecules differs from their less crystalline counterparts. In this work, two families of organic semiconductor SMs are investigated, where the composition of the crystalline core, the location (side- vs end-functionalization) of the alkyl solubilizing groups, and the constitution (branched vs linear) of the alkyl groups are varied. With these SMs, we present a systematic study of how the phase behavior of the SMs affects the overall assembly of these organic semiconductor-based supramolecules. The incorporation of SMs has a large effect on the interfacial curvature, the supramolecular periodicity, and the overall supramolecular morphology. The crystal packing of the SM within the supramolecule does not necessarily lead to the assembly of the comb block within the BCP microdomains, as is normally observed for alkyl-containing supramolecules. An unusual lamellar morphology with a wavy interface between the microdomains is observed due to changes in the packing structure of the small molecule within BCP microdomains. Since the supramolecular approach is modular and small molecules can be readily switched out, present studies provide useful guidance toward access supramolecular assemblies over several length scales using optically active and semiconducting small molecules.},
doi = {10.1021/acs.macromol.5b02449},
journal = {Macromolecules},
number = 3,
volume = 49,
place = {United States},
year = {Thu Jan 21 00:00:00 EST 2016},
month = {Thu Jan 21 00:00:00 EST 2016}
}
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