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Influence of Terminal Carboxyl Group on Structure and Reactivity of Functionalized m-Carboranethiolate Self-Assembled Monolayers
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SYSNO ASEP 0525516 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Influence of Terminal Carboxyl Group on Structure and Reactivity of Functionalized m-Carboranethiolate Self-Assembled Monolayers Author(s) Goronzy, D. P. (US)
Staněk, Jan (UACH-T)
Avery, E. (US)
Guo, H. (US)
Bastl, Zdeněk (UFCH-W) RID, ORCID
Dušek, Michal (FZU-D) RID, ORCID, SAI
Gallup, N. (US)
Gün, S. (TR)
Kučeráková, Monika (FZU-D) RID, ORCID
Levandowski, B.J. (US)
Macháček, Jan (UACH-T) RID, ORCID, SAI
Šícha, Václav (UACH-T) RID, ORCID, SAI
Thomas, J. C. (US)
Yavuz, A. (TR)
Houk, K. (US)
Danişman, M.F. (TR)
Mete, E. (TR)
Alexandrova, A. N. (US)
Baše, Tomáš (UACH-T) RID, SAI, ORCID
Weiss, P. S. (US)Number of authors 20 Source Title Chemistry of Materials. - : American Chemical Society - ISSN 0897-4756
Roč. 32, č. 15 (2020), s. 6800-6809Number of pages 10 s. Language eng - English Country US - United States Keywords Monolayers ; Carboxyls ; Thiols ; Molecular structure Subject RIV CA - Inorganic Chemistry OECD category Inorganic and nuclear chemistry Subject RIV - cooperation J. Heyrovsky Institute of Physical Chemistry - Physical ; Theoretical Chemistry
Institute of Physics - Solid Matter Physics ; MagnetismR&D Projects LTAIN19152 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) TH02020628 GA TA ČR - Technology Agency of the Czech Republic (TA ČR) GA18-10438S GA ČR - Czech Science Foundation (CSF) Method of publishing Limited access Institutional support UACH-T - RVO:61388980 ; UFCH-W - RVO:61388955 ; FZU-D - RVO:68378271 UT WOS 000562136900054 EID SCOPUS 85091037649 DOI 10.1021/acs.chemmater.0c02722 Annotation The structure and function of self-assembled monolayers (SAMs) at the nanoscale are determined by the steric and electronic effects of their building blocks. Carboranethiol molecules form pristine monolayers that provide tunable two-dimensional systems to probe lateral and interfacial interactions. Additional ω-functionality, such as carboxyl groups, can be introduced to change the properties of the exposed surfaces. Here, two geometrically similar isomeric m-carborane analogs of m mercaptobenzoic acid, 1 COOH-7-SH-1,7-C2B10H10 and racem-1-COOH-9-SH-1,7-C2B10H10, are characterized and their SAMs on Au{111} are examined. The latter isomer belongs to the rare group of chiral cage molecules and becomes, to our knowledge, the first example assembled on Au{111}. Although different in symmetry, molecules of both isomers assemble into similar hexagonal surface patterns. The nearest neighbor spacing of 8.4 ± 0.4 Å is larger than that of non-carboxylated isomers, consistent with the increased steric demands of the carboxyl groups. Computational modeling reproduced this spacing and suggests a tilt relative to the surface normal. However, tilt domains are not observed experimentally, suggesting the presence of strong lateral interactions. Analyses of the influence of the functional groups through the pseudo-aromatic m carborane skeleton showed that the thiol group attached to either carbon or boron atoms increases the carboxyl group acidity in solution. In contrast, the acidity of the exposed carboxyl group in the SAMs decreases upon surface attachment, computational analyses suggest that the driving force of this shift is the dielectric of the environment in the monolayer as a result of confined intermolecular interactions, proximity to the Au surface, and partial desolvation. Workplace Institute of Inorganic Chemistry Contact Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Year of Publishing 2021 Electronic address https://pubs.acs.org/doi/10.1021/acs.chemmater.0c02722
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