Tuning Structure-Function Properties of π-Conjugated Superstructures by Redox-Assisted Self-Assembly

Kaixuan Liu, Adam Levy, Chuan Liu, Jean Hubert Olivier

Research output: Contribution to journalArticlepeer-review

14 Scopus citations


Controlling structure-function properties of hierarchical assemblies that feature stacks of π-conjugated building blocks represents an important challenge to engineer optoelectronic materials. In this regard, the development of new tools to navigate the free energy landscape of supramolecular assembly can lead to the creation of kinetically trapped superstructures equipped with emergent electronic properties. In the present contribution, we demonstrate that redox-assisted self-assembly of supramolecular polymers built from water-soluble perylene diimide enforces formation of superstructures with optoelectronic properties not manifested in parent assemblies. Leveraging on a theoretical model developed for H-aggregates in semiconducting polymers, free-exciton bandwidth has been calculated and increases by more than 30% in kinetically trapped superstructures (380 meV) when compared to initially prepared assemblies (290 meV). Electronic structure of intermediate assemblies is believed to perturb intermolecular interactions that regulate the conformation of initially prepared architectures. In addition to offering a means to modulate superstructure electronic properties, intermediate states can be further manipulated by thermal treatment to enable the formation of hierarchical nano-to-mesoscale materials. Investigation of their solid-state morphologies using atomic force microscopy reveals long aspect ratio nanowires spanning micro-to-mesoscale dimensions. Such morphological changes combined with novel electronic properties indicate that structure-function properties of supramolecular constructs can be modulated by redox-assisted self-assembly.

Original languageEnglish (US)
Pages (from-to)2143-2150
Number of pages8
JournalChemistry of Materials
Issue number6
StatePublished - Mar 27 2018

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry


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