Formation and dissociation of intra-intermolecular hydrogen-bonded solute-solvent complexes

Chemical exchange two-dimensional infrared vibrational echo spectroscopy

Junrong Zheng, Kyungwon Kwak, Xin Chen, John B. Asbury, M. D. Fayer

Research output: Contribution to journalArticle

66 Citations (Scopus)

Abstract

2-Methoxyphenol (2MP) solutes form weak complexes with toluene solvent molecules. The complexes are unusual in that the 2MP hydroxyl has an intramolecular hydrogen bond and simultaneously forms an intermolecular hydrogen bond with toluene and other aromatic solvents. In the equilibrated solute-solvent solution, there exists approximately the same concentration of 2MP-toluene complex and free 2MP. The very fast formation and dissociation (chemical exchange) of this type of three-centered hydrogen bond complex were observed in real time under thermal equilibrium conditions with two-dimensional (2D) infrared vibrational echo spectroscopy. Chemical exchange is manifested in the 2D spectrum by the growth of off-diagonal peaks. Both the formation and dissociation can be characterized in terms of the dissociation time constant, which was determined to be 3 ps for the 2MP-toluene complex. The intra-intermolecular hydrogen bond formation is influenced by subtle details of the molecular structure. Although 2MP forms a complex with toluene, it is demonstrated that 2-ethoxyphenol (2EP) does not form complexes to any significant extent. Density functional calculations at the B3LYP/6-31 +G(d,p) level suggest that steric effects caused by the extra methyl group in 2EP are responsible for the difference.

Original languageEnglish
Pages (from-to)2977-2987
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number9
DOIs
Publication statusPublished - 2006 Mar 8
Externally publishedYes

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Guaiacol
Toluene
Hydrogen
Spectrum Analysis
Spectroscopy
Infrared radiation
Hydrogen bonds
Molecular structure
Density functional theory
Molecular Structure
Ion exchange
Hydroxyl Radical
Hot Temperature
Molecules
Growth

ASJC Scopus subject areas

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

Cite this

Formation and dissociation of intra-intermolecular hydrogen-bonded solute-solvent complexes : Chemical exchange two-dimensional infrared vibrational echo spectroscopy. / Zheng, Junrong; Kwak, Kyungwon; Chen, Xin; Asbury, John B.; Fayer, M. D.

In: Journal of the American Chemical Society, Vol. 128, No. 9, 08.03.2006, p. 2977-2987.

Research output: Contribution to journalArticle

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