Controlled self-assembly of pi-stacked/H-bonded 1D crystal structures from polyfluorinated arylamines and 18-crown-6 (2:1). Associate vs. co-former fluorescence properties

Controlled self-assembly of pi-stacked/H-bonded 1D crystal structures from polyfluorinated arylamines and 18-crown-6 (2:1). Associate vs. co-former fluorescence properties Full article

Journal

CrystEngComm
ISSN: 1466-8033

Output data

Year: 2018, Volume: 20, Number: 6, Pages: 807-817 Pages count : 11 DOI: 10.1039/c7ce01851g

Authors

Vaganova Tamara A. ¹ , Gatilov Yurij V. ^1,2 , Pishchur Denis P. ³ , Chuikov Igor P. ¹ , 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) Novosibirsk State Univ, Pirogov Ave 2, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, 3 Lavrentiev Ave, Novosibirsk 630090, Russia

Supramolecular 1D assemblies supported by N-H center dot center dot center dot O-cr and p-stacking interactions were designed and synthesized using polyfluorinated arylamines, differing in the nature of the aromatic ring (benzene, naphthalene, pyridine) and para-substituents (H, F, CN, CF3), and 18-crown-6 ether. Co-crystal structures and intermolecular interactions were studied in detail using X-ray analysis and compared with those in individual arylamine crystals. In the co-crystals, all relatively weak H-bonds N-H. X (X = F, N-het, N-cyano) are replaced by the stronger bond N-H center dot center dot center dot O-crown and pi-stacking in pairs of the arylamine molecules is realized. Depending on the arylamine structure, a parallel displaced, rotated, or slipped stack geometry occurs. Using DSC, phase transitions in the co-crystals were determined and the thermal characteristics were found to be reproduced in the melting-crystallization cycles, which indicates the regeneration of the crystal structure. For a number of compounds, there are significant changes in the fluorescence characteristics, in terms of both intensity and wavelength, due to the formation of associates with 18-crown-6: aggregation-induced emission in the pentafluoroaniline associate, a large shift of lambda(em) in the 4-cyanotetrafluoroaniline associate, and aggregation-caused quenching in the 4-aminotetrafluoropyridine associate. Crystal structure analysis reveals that p-stacking interactions between arylamines play a key role in the modulation of the solid-state fluorescence properties. The revealed effect of fluorescence build-up/quenching shows these types of supramolecular associates to be promising solid-state chemosensors.

Vaganova T.A. , Gatilov Y.V. , Pishchur D.P. , Chuikov I.P. , Malykhin E.V.
Controlled self-assembly of pi-stacked/H-bonded 1D crystal structures from polyfluorinated arylamines and 18-crown-6 (2:1). Associate vs. co-former fluorescence properties
CrystEngComm. 2018. V.20. N6. P.807-817. DOI: 10.1039/c7ce01851g WOS Scopus РИНЦ

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