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: Article (Published version)
Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes.
Exportado de SIDERAL (2024-03-01-14:52:58)
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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: Article (Published version)
Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. Exportado de SIDERAL (2024-03-01-14:52:58)
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Record created 2024-03-01, last modified 2024-03-01