skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Self-Assembly and Orientation of Hydrogen-Bonded Oligothiophene Polymorphs at Liquid-Membrane-Liquid Interfaces

Abstract

One of the challenges in organic systems with semiconducting function is the achievement of molecular orientation over large scales. We report here on the use of self-assembly kinetics to control long-range orientation of a quarterthiophene derivative designed to combine intermolecular π-π stacking and hydrogen bonding among amide groups. Assembly of these molecules in the solution phase is prevented by the hydrogen-bond-accepting solvent tetrahydrofuran, whereas formation of H-aggregates is facilitated in toluene. Rapid evaporation of solvent in a solution of the quarterthiophene in a 2:1:1 mixture of 1,4-dioxane/tetrahydrofuran/toluene leads to self-assembly of kinetically trapped mats of bundled fibers. In great contrast, slow drying in a toluene atmosphere leads to the homogeneous nucleation and growth of ordered structures shaped as rhombohedra or hexagonal prisms depending on concentration. Furthermore, exceedingly slow delivery of toluene from a high molecular weight polymer solution into the system through a porous aluminum oxide membrane results in the growth of highly oriented hexagonal prisms perpendicular to the interface. The amide groups of the compound likely adsorb onto the polar aluminum oxide surface and direct the self-assembly pathway toward heterogeneous nucleation and growth to form hexagonal prisms. We propose that the oriented prismatic polymorph results from the synergy ofmore » surface interactions rooted in hydrogen bonding on the solid membrane and the slow kinetics of self-assembly. These observations demonstrate how self-assembly conditions can be used to guide the supramolecular energy landscape to generate vastly different structures. These fundamental principles allowed us to grow oriented prismatic assemblies on transparent indium-doped tin oxide electrodes, which are of interest in organic electronics.« less

Authors:
; ; ; ; ;  [1]
  1. NWU
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1034182
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 133; Journal Issue: (41) ; 10, 2011; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
08 HYDROGEN; ALUMINIUM; AMIDES; BONDING; DRYING; ELECTRODES; HYDROGEN; KINETICS; MEMBRANES; MIXTURES; MOLECULAR WEIGHT; NUCLEATION; ORIENTATION; OXIDES; POLYMERS; PRISMS; SOLVENTS; TETRAHYDROFURAN; TIN OXIDES; TOLUENE

Citation Formats

Tevis, Ian D, Palmer, Liam C, Herman, David J, Murray, Ian P, Stone, David A, and Stupp, Samuel I. Self-Assembly and Orientation of Hydrogen-Bonded Oligothiophene Polymorphs at Liquid-Membrane-Liquid Interfaces. United States: N. p., 2012. Web. doi:10.1021/ja204811b.
Tevis, Ian D, Palmer, Liam C, Herman, David J, Murray, Ian P, Stone, David A, & Stupp, Samuel I. Self-Assembly and Orientation of Hydrogen-Bonded Oligothiophene Polymorphs at Liquid-Membrane-Liquid Interfaces. United States. doi:10.1021/ja204811b.
Tevis, Ian D, Palmer, Liam C, Herman, David J, Murray, Ian P, Stone, David A, and Stupp, Samuel I. Thu . "Self-Assembly and Orientation of Hydrogen-Bonded Oligothiophene Polymorphs at Liquid-Membrane-Liquid Interfaces". United States. doi:10.1021/ja204811b.
@article{osti_1034182,
title = {Self-Assembly and Orientation of Hydrogen-Bonded Oligothiophene Polymorphs at Liquid-Membrane-Liquid Interfaces},
author = {Tevis, Ian D and Palmer, Liam C and Herman, David J and Murray, Ian P and Stone, David A and Stupp, Samuel I},
abstractNote = {One of the challenges in organic systems with semiconducting function is the achievement of molecular orientation over large scales. We report here on the use of self-assembly kinetics to control long-range orientation of a quarterthiophene derivative designed to combine intermolecular π-π stacking and hydrogen bonding among amide groups. Assembly of these molecules in the solution phase is prevented by the hydrogen-bond-accepting solvent tetrahydrofuran, whereas formation of H-aggregates is facilitated in toluene. Rapid evaporation of solvent in a solution of the quarterthiophene in a 2:1:1 mixture of 1,4-dioxane/tetrahydrofuran/toluene leads to self-assembly of kinetically trapped mats of bundled fibers. In great contrast, slow drying in a toluene atmosphere leads to the homogeneous nucleation and growth of ordered structures shaped as rhombohedra or hexagonal prisms depending on concentration. Furthermore, exceedingly slow delivery of toluene from a high molecular weight polymer solution into the system through a porous aluminum oxide membrane results in the growth of highly oriented hexagonal prisms perpendicular to the interface. The amide groups of the compound likely adsorb onto the polar aluminum oxide surface and direct the self-assembly pathway toward heterogeneous nucleation and growth to form hexagonal prisms. We propose that the oriented prismatic polymorph results from the synergy of surface interactions rooted in hydrogen bonding on the solid membrane and the slow kinetics of self-assembly. These observations demonstrate how self-assembly conditions can be used to guide the supramolecular energy landscape to generate vastly different structures. These fundamental principles allowed us to grow oriented prismatic assemblies on transparent indium-doped tin oxide electrodes, which are of interest in organic electronics.},
doi = {10.1021/ja204811b},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = (41) ; 10, 2011,
volume = 133,
place = {United States},
year = {2012},
month = {3}
}