Supramolecular Double-Helix Formation by Diastereoisomeric Conformations of Configurationally Enantiomeric Macrocycles

Avik Samanta, Zhichang Liu, Siva Krishna Mohan Nalluri, Yu Zhang, George C Schatz, J. Fraser Stoddart

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Solid-state superstructures, resulting from assemblies programmed by homochirality, are attracting considerable attention. In addition, artificial double-helical architectures are being investigated, especially in relation to the ways in which homochiral small molecules can be induced to yield helical forms as a result of chiral induction. Herein, we report the highly specific self-assembly upon crystallization of a double-helical superstructure from an enantiopure macrocyclic dimer which adopts two diastereoisomeric conformations in a molar ratio of 1.5:1 in dimethyl sulfoxide. These two conformational diastereoisomers self-organize - and self-sort - in the crystalline phase in equimolar proportions to form two single-handed helices which are complementary to each other, giving rise to the assembly of a double helix that is stabilized by intermolecular [C-H···O] and stacking interactions. The observed self-sorting phenomenon occurs on going from a mixed-solvent system containing two equilibrating conformational diastereoisomers, presumably present in unequal molar proportions, into the solid state. The diastereoisomeric conformations are captured upon crystallization in a 1:1 molar ratio in the double-helical superstructure, whose handedness is dictated by the choice of the enantiomeric macrocyclic dimer. The interconversion of the two conformational diastereoisomers derived from each configurationally enantiomeric macrocycle was investigated in CD3SOCD3 solution by variable-temperature 1H NMR spectroscopy (VT NMR) and circular dichroism (VT CD). The merging of the resonances for the protons corresponding to the two diastereoisomers at a range of coalescence temperatures in the VT NMR spectra and occurrence of the isosbestic points in the VT CD spectra indicate that the two diastereoisomers are interconverting slowly in solution on the 1H NMR time scale but rapidly on the laboratory time scale. To the best of our knowledge, the self-assembly of such solid-state superstructures from two conformational diastereoisomers of a homochiral macrocycle is a rare, if not unique, occurrence.

Original languageEnglish
Pages (from-to)14469-14480
Number of pages12
JournalJournal of the American Chemical Society
Volume138
Issue number43
DOIs
Publication statusPublished - Nov 2 2016

Fingerprint

Circular Dichroism
Crystallization
Conformations
Nuclear magnetic resonance
Functional Laterality
Temperature
Dichroism
Dimethyl Sulfoxide
Dimers
Self assembly
Protons
Magnetic Resonance Spectroscopy
Dimethyl sulfoxide
Coalescence
Sorting
Merging
Nuclear magnetic resonance spectroscopy
Crystalline materials
Molecules
Proton Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Supramolecular Double-Helix Formation by Diastereoisomeric Conformations of Configurationally Enantiomeric Macrocycles. / Samanta, Avik; Liu, Zhichang; Nalluri, Siva Krishna Mohan; Zhang, Yu; Schatz, George C; Stoddart, J. Fraser.

In: Journal of the American Chemical Society, Vol. 138, No. 43, 02.11.2016, p. 14469-14480.

Research output: Contribution to journalArticle

Samanta, Avik ; Liu, Zhichang ; Nalluri, Siva Krishna Mohan ; Zhang, Yu ; Schatz, George C ; Stoddart, J. Fraser. / Supramolecular Double-Helix Formation by Diastereoisomeric Conformations of Configurationally Enantiomeric Macrocycles. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 43. pp. 14469-14480.
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