Issue 16, 2024

On the origin of cooperativity effects in the formation of self-assembled molecular networks at the liquid/solid interface

Abstract

In this work we investigate the behaviour of molecules at the nanoscale using scanning tunnelling microscopy in order to explore the origin of the cooperativity in the formation of self-assembled molecular networks (SAMNs) at the liquid/solid interface. By studying concentration dependence of alkoxylated dimethylbenzene, a molecular analogue to 5-alkoxylated isophthalic derivatives, but without hydrogen bonding moieties, we show that the cooperativity effect can be experimentally evaluated even for low-interacting systems and that the cooperativity in SAMN formation is its fundamental trait. We conclude that cooperativity must be a local effect and use the nearest-neighbor Ising model to reproduce the coverage vs. concentration curves. The Ising model offers a direct link between statistical thermodynamics and experimental parameters, making it a valuable tool for assessing the thermodynamics of SAMN formation.

Graphical abstract: On the origin of cooperativity effects in the formation of self-assembled molecular networks at the liquid/solid interface

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Jan 2024
Accepted
12 Mar 2024
First published
14 Mar 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 6076-6087

On the origin of cooperativity effects in the formation of self-assembled molecular networks at the liquid/solid interface

T. Rinkovec, D. Kalebic, W. Dehaen, S. Whitelam, J. N. Harvey and S. De Feyter, Chem. Sci., 2024, 15, 6076 DOI: 10.1039/D4SC00284A

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