Polyfluorinated hydroxy and carboxy benzenes as a new type of H-donors for self-assembly with 18-crown-6 ether: Synthesis, supramolecular structure and stability of co-crystals

Polyfluorinated hydroxy and carboxy benzenes as a new type of H-donors for self-assembly with 18-crown-6 ether: Synthesis, supramolecular structure and stability of co-crystals Full article

Journal

Journal of Fluorine Chemistry
ISSN: 0022-1139

Output data

Year: 2020, Volume: 236, Article number : 109577, Pages count : DOI: 10.1016/j.jfluchem.2020.109577

Tags

Hydroxy and carboxy polyfluorobenzenes; Crown ether; Molecular co-crystals; Supramolecular architecture; Water-mediated H-bonds; X-ray diffraction analysis

Authors

Vaganova Tamara A. ¹ , Gatilov Yurij, V ¹ , Pishchur Denis P. ² , Malykhin Evgenij, V ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, NN Vorozhtsov Novosibirsk Inst Organ Chem, Siberian Branch, 9 Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, 3 Lavrentiev Ave, Novosibirsk 630090, Russia

Potential of polyfluoroaromatic compounds containing OH, COOH, and mixed H-donor functions as co-formers in co-crystallization with 18-crown-6 ether was explored. Pentafluorophenol, 1,3- and 1,4-dihydroxytetrafluorobenzenes and pentafluorobenzoic acid form with 18-crown-6 hydrated co-crystals containing one water molecule per H-donor group upon contact of the solutions with atmospheric moisture; pentafluorophenol gives a co-crystal with double the amount of water in aqueous EtOH. Aminotetrafluorobenzyl alcohol and aminotetrafluorobenzoic acid are capable of forming anhydrous 1:1 and 2:1 co-crystals with 18-crown-6. In the crystalline hydrates, co-formers molecules are connected via water-mediated synthon [C(O)]O-H center dot center dot center dot O(H)-H center dot center dot center dot O-cr. According to quantum chemical calculations, the participation of each water linker molecule in H-bonding increases the stability of the supramolecular structure by about 100 kJ mol(-1). Associates of bifunctional arenes exhibit H-bonded 1D assembly as an only structure-determining motif; molecules of monofunctional arenes in the co-crystals are bound via pi(F)center dot center dot center dot pi(F) stacking to give the H-bonded/pi-stacked 1D assembly. The calculated pi-stacking energy depends on the nature of the H-donor function (NH2, OH, COOH), decreasing with a decrease in the molecule dipole moment.

Vaganova T.A. , Gatilov Y.V. , Pishchur D.P. , Malykhin E.V.
Polyfluorinated hydroxy and carboxy benzenes as a new type of H-donors for self-assembly with 18-crown-6 ether: Synthesis, supramolecular structure and stability of co-crystals
Journal of Fluorine Chemistry. 2020. V.236. 109577 . DOI: 10.1016/j.jfluchem.2020.109577 WOS Scopus РИНЦ

Published print:

Aug 1, 2020

Web of science	WOS:000551145100012
Scopus	2-s2.0-85086110127
Elibrary	43277089
OpenAlex	W3028731211