Synthesis of a preorganized hybrid macrobicycle with distinct amide and amine clefts: Tetrahedral versus spherical anions binding studies

Subrata Saha, Bidyut Akhuli, Sourav Chakraborty, Pradyut Ghosh

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

A new C3v symmetric amido-amine hybrid macrobicycle, L is synthesized toward anion recognition in its protonated states. L contains tri-amide and tetra-amine clefts separated by p-phenylene spacers. The solid-state structure of methanol-encapsulated L exhibits an overall cavity length of ∼12.0 Å where the amide and amine -NH protons are converged toward the center of the respective cavities. Conformational analysis of L in solution is established by NOESY NMR. Anion binding of [H3L] 3+ with spherical (Cl-, Br-, I-) and tetrahedral (ClO4-, SO42-) anions are carried out by isothermal titration calorimeter in dimethylsulfoxide. The association of halides with [H3L]3+ is endothermic and entropy driven. However, association of tetrahedral anions is exothermic in nature and both entropy- and enthalpy-driven. The overall association constants show the following order: HSO4- > Br-> Cl- ≈ ClO4-. Single crystal X-ray structures of ClO4- and Br- complexes of protonated L show encapsulation of ClO4- in the amide cleft of [H 2L]2+ (complex 1) and encapsulation of Br- in the ammonium cleft of [H3L]3+ (complex 2). Further, preorganization of L toward encapsulation of spherical and tetrahedral anions is established by comparing its amide, amine, and overall cavity dimensions with 1 and 2.

Original languageEnglish
Pages (from-to)8759-8765
Number of pages7
JournalJournal of Organic Chemistry
Volume78
Issue number17
DOIs
StatePublished - 6 Sep 2013
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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