Structure and properties of 1,3-phenylenediboronic acid: combined experimental and theoretical investigations

Agnieszka Adamczyk-Woźniak , Michał Cyrański , Krzysztof Durka , Jan T. Gozdalik , Paulina Klimentowska , Rafał Rusiecki , Andrzej Sporzyński , Dorota Zarzeczańska

Abstract

The structure and properties of 1,3-phenylenediboronic acid are reported. Molecular and crystal structures were determined by single crystal as well as by powder X-ray diffraction methods. Acidity constant, thermal behavior, and NMR characterization of the title compound were also investigated. In addition to the experimental data, calculations of rotational barrier and intermolecular interaction energies were performed. The compound reveals a two-step acid–base equilibrium with different pKa values. TGA and DSC measurements show a typical dehydration reaction with formation of boroxine. In crystals, hydrogen-bonded dimers with syn-anti conformation of hydroxyl groups form large numbers of ribbon motifs. The 2D potential energy surface scan of rotation of two boronic groups with respect to phenyl ring reveals that the rotation barrier is close to 37 kJ⋅mol−1, which is higher than the double value for the rotation of the boronic group in phenylboronic acid. This effect was ascribed to intermolecular interaction with C–H hydrogen atom located between boronic groups. Furthermore, the molecules in the crystal lattice adopt a less stable molecular conformation most likely resulting from intermolecular forces. These were further investigated by periodic DFT calculations supported by an estimation of dimer interaction energy, and also by topological analysis of electron density in the framework of AIM theory.
Author Agnieszka Adamczyk-Woźniak
Agnieszka Adamczyk-Woźniak,,
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, Michał Cyrański
Michał Cyrański,,
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, Krzysztof Durka
Krzysztof Durka,,
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, Jan T. Gozdalik
Jan T. Gozdalik,,
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, Paulina Klimentowska
Paulina Klimentowska,,
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, Rafał Rusiecki
Rafał Rusiecki,,
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, Andrzej Sporzyński
Andrzej Sporzyński,,
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, Dorota Zarzeczańska (FCh / DACh / LSCh)
Dorota Zarzeczańska,,
- Laboratory of Supramolecular Chemistry
Journal seriesCrystals, ISSN 2073-4352, (A 20 pkt)
Issue year2019
Vol9
No2
Pages1-16
Keywords in Englishboronic acid, 1,3-phenylenediboronic acid, crystal structure, DSC, TGA, acidity constant, rotation barrier, DFT, AIM
ASJC Classification1604 Inorganic Chemistry; 3104 Condensed Matter Physics; 2500 General Materials Science; 1500 General Chemical Engineering
DOIDOI:10.3390/cryst9020109
URL https://doi.org/10.3390/cryst9020109
Languageen angielski
LicenseJournal (articles only); published final; Uznanie Autorstwa (CC-BY); with publication
Score (nominal)20
ScoreMinisterial score = 20.0, 24-07-2019, ArticleFromJournal
Publication indicators WoS Citations = 0; Scopus SNIP (Source Normalised Impact per Paper): 2017 = 0.745; WoS Impact Factor: 2017 = 2.144 (2) - 2017=1.928 (5)
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