Supramolecular Gelation of Rigid Triangular Macrocycles through Rings of Multiple C-H⋯O Interactions Acting Cooperatively

Zhichang Liu, Junling Sun, Yu Zhou, Yu Zhang, Yilei Wu, Siva Krishna Mohan Nalluri, Yuping Wang, Avik Samanta, Chad A. Mirkin, George C. Schatz, J. Fraser Stoddart

Research output: Contribution to journalArticle

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Abstract

When equimolar solutions of the enantiomeric naphthalenediimide-based highly rigid triangles R-Δ and S-Δ in ClCH2CH2Cl are mixed, the racemate rac-Δ forms an organogel that is composed of interwoven fibers, resulting from the columnar stacking of the triangles in an alternating R-Δ/S-Δ fashion. Under identical conditions, the pure enantiomers do not form organogels. Density functional theory calculations reveal that the racemic RS dimer is more stable than the RR dimer as a result of the enantiomeric relationship between R-Δ and S-Δ, allowing them to act as two complementary rings comprised of 12 [C-H···O] interactions with an unprecedented and uninterrupted circular ADDAADDAADDA·DAADDAADDAAD alignment of hydrogen bond donors (D) and acceptors (A), in contrast with the square-wave manner in which the RR dimer forms a complementary yet interrupted ADADAD·DADADA circular sequence of six longer [C-H⋯O] hydrogen bonds. It follows that gelation is favored by weak interactions acting cooperatively in rings under precise stereoelectronic control.

Original languageEnglish
Pages (from-to)2581-2588
Number of pages8
JournalJournal of Organic Chemistry
Volume81
Issue number6
DOIs
Publication statusPublished - Mar 18 2016

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Gelation
Dimers
Hydrogen bonds
Enantiomers
Density functional theory
Fibers

ASJC Scopus subject areas

  • Organic Chemistry

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Supramolecular Gelation of Rigid Triangular Macrocycles through Rings of Multiple C-H⋯O Interactions Acting Cooperatively. / Liu, Zhichang; Sun, Junling; Zhou, Yu; Zhang, Yu; Wu, Yilei; Nalluri, Siva Krishna Mohan; Wang, Yuping; Samanta, Avik; Mirkin, Chad A.; Schatz, George C.; Stoddart, J. Fraser.

In: Journal of Organic Chemistry, Vol. 81, No. 6, 18.03.2016, p. 2581-2588.

Research output: Contribution to journalArticle

Liu, Z, Sun, J, Zhou, Y, Zhang, Y, Wu, Y, Nalluri, SKM, Wang, Y, Samanta, A, Mirkin, CA, Schatz, GC & Stoddart, JF 2016, 'Supramolecular Gelation of Rigid Triangular Macrocycles through Rings of Multiple C-H⋯O Interactions Acting Cooperatively', Journal of Organic Chemistry, vol. 81, no. 6, pp. 2581-2588. https://doi.org/10.1021/acs.joc.6b00281
Liu, Zhichang ; Sun, Junling ; Zhou, Yu ; Zhang, Yu ; Wu, Yilei ; Nalluri, Siva Krishna Mohan ; Wang, Yuping ; Samanta, Avik ; Mirkin, Chad A. ; Schatz, George C. ; Stoddart, J. Fraser. / Supramolecular Gelation of Rigid Triangular Macrocycles through Rings of Multiple C-H⋯O Interactions Acting Cooperatively. In: Journal of Organic Chemistry. 2016 ; Vol. 81, No. 6. pp. 2581-2588.
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