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

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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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ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Liu, Z., Sun, J., Zhou, Y., Zhang, Y., Wu, Y., Nalluri, S. K. M., Wang, Y., Samanta, A., Mirkin, C. A., Schatz, G. C., & Stoddart, J. F. (2016). Supramolecular Gelation of Rigid Triangular Macrocycles through Rings of Multiple C-H⋯O Interactions Acting Cooperatively. Journal of Organic Chemistry, 81(6), 2581-2588. https://doi.org/10.1021/acs.joc.6b00281