Molecular mechanisms underlying nanowire formation in pristine phthalocyanine

TitleMolecular mechanisms underlying nanowire formation in pristine phthalocyanine
Publication TypeJournal Article
Year of Publication2023
AuthorsPinjari, A, Saraf, D, Sengupta, D
JournalPhysical Chemistry Chemical Physics
Volume25
Issue44
Pagination30259-30268
Date PublishedNOV
Type of ArticleArticle
ISSN1463-9076
Abstract

Understanding the molecular processes of nanowire self-assembly is crucial for designing and controlling nanoscale structures that could lead to breakthroughs in functional materials. In this work, we focus on pristine phthalocyanines as a representative example of mesogenic supramolecular assemblies and have analyzed the formation of nanowires using classical molecular dynamics simulations. In the simulations, the molecules spontaneously form multi-columnar structures resembling supramolecular polymers that subsequently grow into more ordered aggregates. These self-assemblies are concentration dependent, leading to the formation of multi-columnar, dynamic aggregates at higher concentrations and nanowires at lower concentrations. The multi-columnar assemblies on a whole are more disordered than the nanowires, but have locally ordered domains of parallel facing molecules that can fluctuate while maintaining their overall shape. The nanowire formation at lower concentrations involves the initial interaction and clustering of randomly oriented phthalocyanine molecules, followed by the merging of small clusters into elongated segments and the eventual formation of a stable nanowire. We observe three main conformers in these self-assemblies, the parallel, T-shaped and edge-to-edge stacking of the phthalocyanine dimers. We calculate the underlying free energy landscape and show that the parallel conformers form the most stable configuration which is followed by the T-shaped and edge-to-edge dimer configurations. The findings provide insights into the mechanisms and pathways of nanowire formation and a step towards the understanding of self-assembly processes in supramolecular mesogens. Understanding the molecular processes of nanowire self-assembly of phthalocyanine molecules.

DOI10.1039/d3cp03512c
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

3.3

Divison category: 
Physical and Materials Chemistry
Database: 
Web of Science (WoS)

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