Self-assembly and orientation of hydrogen-bonded oligothiophene polymorphs at liquid-membrane-liquid interfaces

Ian D. Tevis, Liam C. Palmer, David J. Herman, Ian P. Murray, David A. Stone, Samuel I Stupp

Research output: Contribution to journalArticle

40 Citations (Scopus)

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 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.

Original languageEnglish
Pages (from-to)16486-16494
Number of pages9
JournalJournal of the American Chemical Society
Volume133
Issue number41
DOIs
Publication statusPublished - Oct 19 2011

Fingerprint

Liquid membranes
Toluene
Polymorphism
Self assembly
Hydrogen
Prisms
Membranes
Aluminum Oxide
Liquids
Hydrogen Bonding
Hydrogen bonds
Amides
Growth
Nucleation
Aluminum
Atmosphere
Indium
Kinetics
Oxides
Molecular orientation

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Self-assembly and orientation of hydrogen-bonded oligothiophene polymorphs at liquid-membrane-liquid interfaces. / Tevis, Ian D.; Palmer, Liam C.; Herman, David J.; Murray, Ian P.; Stone, David A.; Stupp, Samuel I.

In: Journal of the American Chemical Society, Vol. 133, No. 41, 19.10.2011, p. 16486-16494.

Research output: Contribution to journalArticle

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. In: Journal of the American Chemical Society. 2011 ; Vol. 133, No. 41. pp. 16486-16494.
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