TY - JOUR

T1 - Controlled self-assembly of π-stacked/H-bonded 1D crystal structures from polyfluorinated arylamines and 18-crown-6 (2

T2 - 1). Associate: Vs. co-former fluorescence properties

AU - Vaganova, Tamara A.

AU - Gatilov, Yurij V.

AU - Pishchur, Denis P.

AU - Chuikov, Igor P.

AU - Malykhin, Evgenij V.

PY - 2018/2/7

Y1 - 2018/2/7

N2 - Supramolecular 1D assemblies supported by N-H⋯Ocr and π-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, Nhet, Ncyano) are replaced by the stronger bond N-H⋯Ocrown and π-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 λem in the 4-cyanotetrafluoroaniline associate, and aggregation-caused quenching in the 4-aminotetrafluoropyridine associate. Crystal structure analysis reveals that π-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.

AB - Supramolecular 1D assemblies supported by N-H⋯Ocr and π-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, Nhet, Ncyano) are replaced by the stronger bond N-H⋯Ocrown and π-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 λem in the 4-cyanotetrafluoroaniline associate, and aggregation-caused quenching in the 4-aminotetrafluoropyridine associate. Crystal structure analysis reveals that π-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.

KW - SOLID-STATE FLUORESCENCE

KW - CROWN-ETHERS

KW - 1,4,7,10,13,16-HEXAOXACYCLOOCTADECANE 18-CROWN-6

KW - COCRYSTAL STRATEGY

KW - ANHYDROUS AMMONIA

KW - PHASE-TRANSITION

KW - CHARGE-TRANSFER

KW - LIQUID-AMMONIA

KW - HYDROGEN-BONDS

KW - COMPLEXES

UR - http://www.scopus.com/inward/record.url?scp=85041653538&partnerID=8YFLogxK

U2 - 10.1039/c7ce01851g

DO - 10.1039/c7ce01851g

M3 - Article

AN - SCOPUS:85041653538

VL - 20

SP - 807

EP - 817

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 6

ER -