Crown Ether–Promoted Helical Self-Assembly of Achiral Molecules: Symmetry Breaking in Cocrystallization of Octafluorobenzidine with 18-Crown-6
Vaganova T. Gatilov Y. Benassi E. Fan H. Pishchur D. Malykhin E.
10 November 2025John Wiley and Sons Inc
ChemPlusChem
2025#90Issue 11
New H-bonded supramolecular assembliesare obtained using the polyfluorobiphenyl H-donor derivatives and 18-crown-6 ether. Cocrystals of octafluorobenzidine with 18-crown-6 of 1:1 stoichiometry belong to the enantiomorphous space groups P65 and P61. The helical self-assembly of these achiral molecules is achieved due to the interplanar angle of the bis-aryl molecule (≈60°), which is fixed by directed N–H···Ocr H-bonds between two Hamino atoms with two Ocr atoms at both ends of the molecule. Cocrystallization of octafluorobiphenol results in the formation of a crystalline hydrate based on the water-mediated H-bond Ar-O-H···O(H)-H···Ocr. Flexible water linker eliminates the effect of the H-donor coformer structure and makes this cocrystal achiral. The hydrogen bonding details between octafluorobenzidine and 18-crown-6 within a unit cell are investigated through a combination of vibrational spectroscopy and quantum mechanical calculations. An oxygen atom in 18-crown-6 is identified as a chiral center, as a result of intermolecular interactions involving this atom and hydrogen atoms bonded to its α and β carbon atoms. The unique interaction patterns of 18-crown-6 with acetone and chloroform, along with scanning electron microscopic images, reveal the role of solvent molecules in determining the chirality of the self-assembly.
acentric self-assembly , computational chemistry , crown compounds , molecular cocrystals , octafluorobenzidine
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Laboratory of Heterocyclic Compounds, N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation
Center of Spectral Research, N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation
Infochemistry Scientific Center, ITMO University, Saint-Petersburg, 191002, Russian Federation
Department of Chemistry, School of Sciences and Humanities, Nazarbayev University, Qabanbay Batyr 53, Nursultan, 010000, Kazakhstan
Laboratory of Physical Chemistry of Condensed Matter, Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation
Laboratory of Heterocyclic Compounds
Center of Spectral Research
Infochemistry Scientific Center
Department of Chemistry
Laboratory of Physical Chemistry of Condensed Matter
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