journal article·2024-02-27Open access

Competing Intermolecular and Molecule–Surface Interactions: Dipole–Dipole-Driven Patterns in Mixed Carborane Self-Assembled Monolayers

Katherine E. White, Erin M. Avery, Edison Cummings, Zixiang Hong, Jens Langecker, Aliaksei Vetushka, Michal Dušek, Jan Macháček, Jakub Višnák, Jan Endres, Zdeněk Bastl, Ersen Mete, Anastassia N. Alexandrova, Tomáš Baše, Paul S. Weiss

Chemistry of Materials· Volume 36· Issue 4

Abstract

Carboranedithiol isomers adsorbing with opposite orientations of their dipoles on surfaces are self-assembled together to form mixed monolayers where both lateral dipole–dipole and lateral thiol–thiolate (S–H···S) interactions provide enhanced stability over single-component monolayers. We demonstrate the first instance of the ability to map individual isomers in a mixed monolayer using the model system carboranedithiols on Au{111}. The addition of methyl groups to one isomer provides both an enhanced dipole moment and extra apparent height for differentiation via scanning tunneling microscopy (STM). Associated computational investigations rationalize favorable interactions of mixed pairs and the associated stability changes that arise from these interactions. Both STM images and Monte Carlo simulations yield similarly structured mixed monolayers, where approximately 10% of the molecules have reversed dipole moment orientations but no direct chemical attachment to the surface, leading to homogeneous monolayers with no apparent phase separation. Deprotonating the thiols by depositing the molecules under basic conditions eliminates the lateral S–H···S interactions while accentuating the dipole–dipole forces. The molecular system investigated is composed of isomeric molecules with opposite orientations of dipoles and identical surface packing, which enables the mapping of individual molecules within the mixed monolayers and enables analyses of the contributions of the relatively weak lateral interactions to the overall stability of the assemblies.
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Research context

OpenAlex topics: Molecular Junctions and Nanostructures · Force Microscopy Techniques and Applications · Advanced Electron Microscopy Techniques and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States

California NanoSystems Institute, University of California, Los Angeles, Los Angeles, California 90095, United States

The Czech Academy of Sciences, Institute of Inorganic Chemistry, c.p. 1001, Husinec-Rez250 68, Czech Republic

The Czech Academy of Sciences, Institute of Physics, Na Slovance 1999/2, 182 21 Prague 8, Czech Republic

Department of Chemistry, Middle East Technical University, Ankara 06800, Turkey

Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 2026/5, 121 16 Praha 2, Czech Republic

The Czech Academy of Sciences, J. Heyrovsky Institute of Physical Chemistry, Dolejskova 3, 182 23 Prague 8, Czech Republic

Department of Physics, Balikesir University, Balikesir 10145, Turkey

Department of Materials Science and Engineering, University of California, Los Angeles, Los Angeles, California 90095, United States

Department of Bioengineering, University of California, Los Angeles, Los Angeles, California 90095, United States

Funding

Division of Chemistry · Basic Energy Sciences · US-UK Fulbright Commission · European Regional Development Fund · Ministerstvo ?kolstv?, Ml?de?e a Telov?chovy · Office of Advanced Cyberinfrastructure · T?rkiye Bilimsel ve Teknolojik Arastirma Kurumu

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