Inclusion complexes of the bicyclic aryl-substituted sulfur-nitrogen compounds Ar-CN5S3 with fluorocarbon and hydrocarbon aromatics

Inclusion complexes of the bicyclic aryl-substituted sulfur-nitrogen compounds Ar-CN5S3 with fluorocarbon and hydrocarbon aromatics Full article

Journal

European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682

Output data

Year: 2004, Number: 12, Pages: 2446-2451 Pages count : 6 DOI: 10.1002/ejic.200300951

Tags

π-Stacking interactions; Crystal engineering; Inclusion compounds; Molecular recognition; Polyfluoroaromatic compounds

Authors

Knapp C. ¹ , Lork E. ¹ , Mews R. ¹ , Zibarev A.V. ²

Affiliations

1	(Scopus) Inst. for Inorg. and Phys. Chemistry, University of Bremen, 28334 Bremen, Germany
2	(Scopus) Institute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation

Inclusion compounds with a stoichiometry of 2:1 were prepared from 7-Ar-1λ4,3λ4,5λ4-trithia- 2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes Ar-CN 5S3 and hexafluorobenzene (Ar = C6H 5, 4-CH3C6H4, 4-C6H 5C6H4 and 2,6-F2C6H 3) and toluene (Ar = C6F5), by crystallization of the bicycles from the corresponding aromatics. Similar to the pure host compounds, the bicycles in the inclusion compounds form centrosymmetric dimers. The packing of the dimers in the pure host compounds is dominated by the interaction of the substituents at the aryl groups, and in the inclusion compounds by the interaction of the host and guest. The parallel-displaced arrangement of the aromatic rings of the host and guest is typical of non-covalent π-stacking interactions of the arene-polyfluroarene type. The inability of benzene (in contrast to hexafluorobenzene) to form an inclusion compound with the title bicycle (Ar = C6H5) indicates that inclusion is driven by π-stacking interactions of the arene-polyfluoroarene type. Crystallization of the title bicycle (Ar = C6H5) from a 1:1 molar mixture of benzene and hexafluorobenzene gave the same inclusion compound as the crystallization from pure hexafluorobenzene. This can be considered as molecular recognition based on π-stacking interactions. The compounds prepared provide the first example of aromatic units bearing extremely sterically demanding polyheteroatom bicyclic substituents involved in non-covalent arene-polyfluoroarene π-stacking interactions. Attempts to prepare inclusion compounds with octafluoronaphthalene and decafluorobiphenyl, as well as co-crystals of para-tolyl- and pentafluorophenyl-substituted bicycles, failed. The origin of the 2:1 stoichiometry and the lack of inclusion in the case of C12F10 and C10F8 are discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Knapp C. , Lork E. , Mews R. , Zibarev A.V.
Inclusion complexes of the bicyclic aryl-substituted sulfur-nitrogen compounds Ar-CN5S3 with fluorocarbon and hydrocarbon aromatics
European Journal of Inorganic Chemistry. 2004. N12. P.2446-2451. DOI: 10.1002/ejic.200300951 WOS Scopus РИНЦ

Published print:

Jun 1, 2004

Web of science	WOS:000222330800007
Scopus	2-s2.0-4544239780
Elibrary	13463176
OpenAlex	W2023469425