Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing

Rancatore, Benjamin J.; Kim, BongSoo; Mauldin, Clayton E.; Fréchet, Jean J.; Xu, Ting

doi:10.1021/acs.macromol.5b02449

Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing

Journal Article · Wed Jan 20 23:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b02449· OSTI ID:1240182

Rancatore, Benjamin J. ^[1]; Kim, BongSoo ^[2]; Mauldin, Clayton E. ^[1]; Fréchet, Jean J. ^[3]; Xu, Ting ^[1]

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)

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.

View Accepted Manuscript (DOE)

Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1240182

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 3 Vol. 49; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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