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

Rinkovec, Tamara; Kalebic, Demian; Dehaen, Wim; Whitelam, Stephen; Harvey, Jeremy N.; De Feyter, Steven

doi:10.1039/d4sc00284a

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

Journal Article · 13 March 2024 · Chemical Science

DOI: https://doi.org/10.1039/d4sc00284a · OSTI ID:2470664

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Katholieke Univ. Leuven (Belgium)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2470664

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 16 Vol. 15; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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

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