Quantifying intrinsic ion-driven conformational changes in diphenylacetylene supramolecular switches with cryogenic ion vibrational spectroscopy

Arron B. Wolk, Etienne Garand, Ian M. Jones, Andrew D. Hamilton, Mark A. Johnson

Research output: Contribution to journalArticlepeer-review

Abstract

We report how two flexible diphenylacetylene (DPA) derivatives distort to accommodate both cationic and anionic partners in the binary X ±·DPA series with X = TMA+ (tetramethylammonium), Na+, Cl-, Br-, and I-. This is accomplished through theoretical analysis of X ±·DPA·2D2 vibrational spectra, acquired by predissociation of the weakly bound D2 adducts formed in a 10 K ion trap. DPA binds the weakly coordinating TMA+ ion with an arrangement similar to that of the neutral compound, whereas the smaller Na + ion breaks all intramolecular H-bonds yielding a structure akin to the transition state for interconversion of the two conformations in neutral DPA. Halides coordinate to the urea NH donors in a bidentate H-bonded configuration analogous to the single intramolecular H-bonded motif identified at high chloride concentrations in solution. Three positions of the "switch" are thus identified in the intrinsic ion accommodation profile that differ by the number of intramolecular H-bonds (0, 1, or 2) at play.

Original languageEnglish (US)
Pages (from-to)5962-5969
Number of pages8
JournalJournal of Physical Chemistry A
Volume117
Issue number29
DOIs
StatePublished - Jul 25 2013

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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