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This work was supported by the MINECO-FEDER funds PGC2018-097583-B-I00, PID2021-122882NB-I00 and PID2021-126132-NB-I00 (MCIN/AEI/10.13039/501100011033/and by "ERDF A way of making Europe") and Gobierno de Aragon-FEDER (Research Group E47_23R). A. C. acknowledges grant RYC2021-031154-I funded by the MICINN/AEI/FEDER/EU-NextGenerationEU. The authors would like to acknowledge the use of the SAI (UZ), CEQMA (UZ-CSIC) Services and the Laboratorio de Microscopias Avanzadas-LMA (INMA-UZ).

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Hydantoin hexameric rosettes: harnessing H-bonds for supergelation and liquid crystals

Publicado en:Organic Chemistry Frontiers. 11 (3): 735-745 - 2023-12-04 11(3), DOI: 10.1039/d3qo01832f

Autores: Gonzalez, Lucia; Marin, Ivan; Tejedor, Rosa M; Barbera, Joaquin; Romero, Pilar; Concellon, Alberto; Uriel, Santiago; Serrano, Jose L

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Resumen

We have synthesized two geometric isomers of a cyclohexane-5-spirohydantoin derivative (1,3-diazaspiro[4.5]decane-2,4-dione) incorporating a hydrophobic phenyl 3,4,5-tris(dodecyloxy)benzoate unit at position 8. Separation of these diastereomers was accomplished through silica gel flash chromatography. The interplay of intermolecular hydrogen bonding and micro-segregation between the polar hydantoin unit and nonpolar aliphatic chains within the molecule endows them with remarkable self-assembly capabilities, both in solution and in the solid state. These hydantoin derivatives spontaneously form rosette-shaped structures composed of six molecules. In the solid state, these compounds display hexagonal columnar liquid crystal phases, with hydrogen-bonded disks as their fundamental building blocks. Similarly, when exposed to apolar solvents such as cyclohexane or dodecane, they adopt a columnar arrangement, resulting in gel formation comprising nanoscale fibers that intricately interlace to form a network. Remarkably, the two isomers exhibit markedly different properties. The major isomer behaves as a glassy liquid crystalline material, while the minor one exhibits liquid crystalline behavior with a high propensity to crystallize. Our experimental findings, in combination with theoretical studies, underscore the fundamentally distinct supramolecular organizations present in these isomers, shedding light on their unique self-assembling properties. We present two hydantoin isomers that self-assemble through hydrogen bonding in solution and in bulk, either in a bowl-shaped or planar rosette, resulting in remarkable liquid crystals and gelation properties.

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