Insight into the Self-Assembly of Water-Soluble Perylene Bisimide Derivatives Through a Combined Computational and Experimental Approach

18 April 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

We use a combination of computational and experimental techniques to study the self-assembly and gelation of water-soluble perylene bisimides derivatised at the imide position with an amino acid. Specifically, we study the likely structure of self-assembled aggregates of the alanine-functionalised perylene bisimide (PBI-A) and the thermodynamics of their formation using density functional theory and predict the UV-vis spectra of such aggregates using time-dependent density functional theory. We compare these predictions to experiments in which we study the evolution of the UV-Vis and NMR spectra and rheology of alkaline PBI-A solutions when gradually decreasing the pH. Based on the combined computational and experimental results, we show that PBI-A self-assembles at all pH values but that aggregates grow in size upon protonation. Gelation is driven not by aggregate growth but reduction of the aggregation surface-charge and a decrease in the colloidal stability of the aggregation with respect to agglomeration.

Keywords

perylene bisimide
perylene diimide
low molecular weight gel
hydrogel
density functional theory

Supplementary materials

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PBI ala theory exp ESI ChemRxiv
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PBI ala theory exp comp data
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PBI ala theory exp exp data
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