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

González, Lucía ; Marín, Iván (Universidad de Zaragoza) ; Tejedor, Rosa M. (Universidad de Zaragoza) ; Barberá, Joaquín (Universidad de Zaragoza) ; Romero, Pilar ; Concellón, Alberto (Universidad de Zaragoza) ; Uriel, Santiago (Universidad de Zaragoza) ; Serrano, José L.

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.

Idioma: Inglés

DOI: 10.1039/D3QO01832F

Año: 2024

Publicado en: ORGANIC CHEMISTRY FRONTIERS 11, 3 (2024), 735-745
ISSN: 2052-4129

Financiación: info:eu-repo/grantAgreement/ES/DGA/E47-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RYC2021-031154-I
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-097583-B-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/PID2021-122882NB-I00

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)