Ground-State Charge-Density Distribution in a Crystal of the Luminescentortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline

Katarzyna N. Jarzembska , Radosław Kamiński , Krzysztof Durka , Krzysztof Woźniak

Abstract

This contribution is devoted to the first electron density studies of a luminescent oxyquinolinato boron complex in the solid state. ortho-Phenylenediboronic acid mixed with 8-hydroxyquinoline in dioxane forms high-quality single crystals via slow solvent evaporation, which allows successful high resolution data collection (sin θ/λ = 1.2 Å–1) and charge density distribution modeling. Particular attention has been paid to the boron–oxygen fragment connecting the two parts of the complex, and to the solvent species exhibiting anharmonic thermal motion. The experiment and theory compared rather well in terms of atomic charges and volumes, except for the boron centers. Boron atoms, as expected, constitute the most electron-deficient species in the complex molecule, whereas the neighboring oxygen and carbon atoms are the most significantly negatively charged ones. This part of the molecule appears to be very much involved in the charge transfer occurring between the acid fragment and oxyquinoline moiety leading to the observed fluorescence, as supported by the time-dependent density functional theory (TDDFT) results and the generated transition density maps. TDDFT calculations indicated that p-type atomic orbitals contributing to the HOMO–1, HOMO, and LUMO play the major role in the lowest energy transitions, and enabled further comparison with the charge density features, which is discussed in details. Furthermore, the results confirmed the known fact the Q ligand character is most important for the spectroscopic properties of this class of complexes.
Author Katarzyna N. Jarzembska
Katarzyna N. Jarzembska,,
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, Radosław Kamiński
Radosław Kamiński,,
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, Krzysztof Durka (FC / DPC)
Krzysztof Durka,,
- Department Of Physical Chemistry
, Krzysztof Woźniak
Krzysztof Woźniak,,
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Journal seriesJournal of Physical Chemistry A, ISSN 1089-5639, (A 30 pkt)
Issue year2018
Vol122
No18
Pages4508-4520
Publication size in sheets0.6
DOIDOI:10.1021/acs.jpca.8b00832
URL https://pubs.acs.org/doi/10.1021/acs.jpca.8b00832
Languageen angielski
File
acs.jpca.8b00832.pdf 2.94 MB
Score (nominal)30
ScoreMinisterial score = 30.0, 24-07-2018, ArticleFromJournal
Ministerial score (2013-2016) = 30.0, 24-07-2018, ArticleFromJournal
Publication indicators WoS Impact Factor: 2016 = 2.847 (2) - 2016=2.663 (5)
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