Understanding cooperativity in hydrogen-bond-induced supramolecular polymerization: a density functional theory study

Area of Science:

• Supramolecular chemistry
• Materials science
• Computational chemistry

Background:

• Cooperative self-assembly is crucial for designing functional supramolecular architectures.
• Trialkylbenzene-1,3,5-tricarboxamide (BTA) molecules form ordered one-dimensional supramolecular polymers via hydrogen bonding.

Purpose of the Study:

• To elucidate the molecular mechanism behind the cooperative growth of BTA-based supramolecular polymers.
• To rationalize experimental observations of BTA self-assembly using theoretical methods.

Main Methods:

• Density functional theory (DFT) calculations were employed.
• Analysis focused on electrostatic interactions and electron density redistribution within growing aggregates.

Main Results:

• DFT analysis confirmed that electrostatic interactions are the primary drivers of cooperative growth.
• Nonadditive effects, arising from electron density redistribution, significantly contribute to the stability and growth of the supramolecular polymers.
• The findings provide a molecular-level understanding of the self-assembly process.

Conclusions:

• The cooperative growth of BTA supramolecular polymers is governed by electrostatic interactions and electron density redistribution.
• This understanding facilitates the rational design of novel supramolecular materials with tailored properties.
• Computational modeling is a powerful tool for investigating complex self-assembly phenomena.