Molecular design and characterizations of new calixarene-based gelators of organic fluids

Masayoshi Aoki, Kazuaki Nakashima, Hirosuke Kawabata, Satoru Tsutsui, Seiji Shinkai

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Abstract

We have found that certain calix[n]arenes having long acyl groups at the p-positions (e.g., 5,11,17,23,29,35,41,47-octadodecanoylcalix[8]arene-49,50,51, 52,53,54,55,56-octol: 28C12) act as excellent and unique gelators of various organic solvents (e.g., toluene, carbon tetrachloride, carbon disulfide, hexane, isopropanol, etc.). The sol-gel phase transition temperatures (Tgel) could be determined by the inverted test-tube method or by the DSC method. The change in the aggregation mode at the phase transition temperature was directly observable by an optical microscope: below Tgel the fibrillar network (diameter ca. 1 μm) appeared whereas above Tgel it 'melted' down. It was shown on the basis of these measurements that the sol-gel phase transition occurs reversibly. The spectroscopic studies using 1H NMR and IR spectroscopy and the comparative experiments using the analogues of 28C12 (nine cyclic and six non-cyclic) established that the prerequisites for the formation of the stable organic gels are (i) the intermolecular C=O⋯HO hygrogen-bonding interaction to form the three-dimensional network and (ii) the moderate affinity of gelators with solvent molecules. The results offer important strategies useful for the molecular design of new gelators of organic fluids.

Original languageEnglish
Pages (from-to)347-354
Number of pages8
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number3
Publication statusPublished - 1993
Externally publishedYes

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Calixarenes
Phase transitions
Sol-gels
Fluids
Carbon Disulfide
2-Propanol
Carbon Tetrachloride
Toluene
Hexanes
Organic solvents
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Microscopes
Agglomeration
Gels
Molecules
Experiments

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Molecular design and characterizations of new calixarene-based gelators of organic fluids. / Aoki, Masayoshi; Nakashima, Kazuaki; Kawabata, Hirosuke; Tsutsui, Satoru; Shinkai, Seiji.

In: Journal of the Chemical Society, Perkin Transactions 2, No. 3, 1993, p. 347-354.

Research output: Contribution to journalArticle

Aoki, Masayoshi ; Nakashima, Kazuaki ; Kawabata, Hirosuke ; Tsutsui, Satoru ; Shinkai, Seiji. / Molecular design and characterizations of new calixarene-based gelators of organic fluids. In: Journal of the Chemical Society, Perkin Transactions 2. 1993 ; No. 3. pp. 347-354.
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