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*

*Corresponding author for this work

Research output: Contribution to journalArticle

19 Scopus citations

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 (US)
Pages (from-to)2581-2588
Number of pages8
JournalJournal of Organic Chemistry
Volume81
Issue number6
DOIs
StatePublished - Mar 18 2016

ASJC Scopus subject areas

  • Organic Chemistry

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