Structure and Properties of 1,3-Phenylenediboronic Acid: Combined Experimental and Theoretical Investigations

Agnieszka Adamczyk-Woźniak , Michał K. Cyrański , Krzysztof Durka , Jan 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 (FC / DPC)
Agnieszka Adamczyk-Woźniak,,
- Department Of Physical Chemistry
, Michał K. Cyrański
Michał K. Cyrański,,
-
, Krzysztof Durka (FC / DPC)
Krzysztof Durka,,
- Department Of Physical Chemistry
, Jan Gozdalik (FC / DPC)
Jan Gozdalik,,
- Department Of Physical Chemistry
, Paulina Klimentowska
Paulina Klimentowska,,
-
, Rafał Rusiecki
Rafał Rusiecki,,
-
, Andrzej Sporzyński (FC / DPC)
Andrzej Sporzyński,,
- Department Of Physical Chemistry
, Dorota Zarzeczańska
Dorota Zarzeczańska,,
-
Journal seriesCrystals, ISSN 2073-4352, (A 20 pkt)
Issue year2019
Vol9
No2, 109
Pages1-16
Publication size in sheets5.45
ASJC Classification3 Physical Sciences
DOIDOI:10.3390/cryst9020109
URL https://www.mdpi.com/2073-4352/9/2/109
Languageen angielski
Score (nominal)20
ScoreMinisterial score = 20.0, 17-07-2019, ArticleFromJournal
Publication indicators 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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