Probing the geometries of functional hydrogen bonds in solution by NMR and Combined NMR/UV/Vis spectroscopy

• Applicant: Professor Dr. Hans-Heinrich Limbach
• Subject Area: Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
• Term: from 2008 to 2012
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 89003435

• Final Report Year: 2012

Final Report Abstract

The main results of this project can be summarized as follows. (1) Combined UVNMR spectroscopy has been developed including a two-dimensional UVNMR correlation method. (2) The UV-Vis band frequencies are correlated with the O…H distances. These results can be used in future UV-Vis studies in order to establish the geometries of critical OHO hydrogen bonds. (3) NMR hydrogen bond correlation methods have been extended to obtain information about geometries of OHO hydrogen bonds from NMR parameters, in particular 1H and 13C chemical shifts. (4) It has been shown that UVNMR, and in cases where chromophores are absent only NMR, provides information about the question of single vs double well proton transfer pathways in stron OHO hydrogen bonds.

Publications

• J. Phys. Chem. A. published online. Hydrogen Bond Geometries and Proton Tautomerism of Homo-Conjugated Anions of Carboxylic Acids Studied via H/D Isotope Effects on 13C NMR Chemical Shifts NMR
  J. Guo, P. M. Tolstoy, B. Koeppe, N. S. Golubev, G. S. Denisov, S. N. Smirnov, H. H. Limbach
  (See online at https://dx.doi.org/10.1021/jp304943h)
• Ang. Chem. Int. Ed. 2009, 48, 5745-5747. Combined NMR/UV-Vis Spectroscopy in the Liquid State: Study of the Geometries of Strong OHO Hydrogen Bonds of Phenols with Carboxylic Acids
  P. M. Tolstoy, B. Koeppe, G. S. Denisov, H. H. Limbach
  
• Israel J. Chem. 2009, 49, 199 - 216. OHO Hydrogen Bond Geometries and NMR Chemical Shifts: From Equilibrium Structures to Geometric H/D Isotope Effects with Applications for Water, Protonated Water and Compressed Ice
  H. H. Limbach, P. Tolstoy, N. Pérez-Hernández, J. Guo, I. G. Shenderovich, G. S. Denisov
  
• J. Phys. Chem. A. 2010, 114, 10775–10782. Geometries and Tautomerism of OHN Hydrogen Bonds in Polar Solution probed by H/D Isotope Effects on 13C NMR Chemical Shifts
  P. M. Tolstoy, J. Guo, B. Koeppe, N. S. Golubev, G. S. Denisov, Sergei N. Smirnov, H. H. Limbach
  
• Ang. Chem. Int. Ed. 2011, 50, 528–531. Encapsulated Carboxylic Acid Dimers with Compressed Hydrogen Bonds
  D. Ajami, P. M. Tolstoy, H. Dube, S. Odermatt, B. Koeppe, J. Guo, H. H. Limbach, J. Rebek, Jr.
  
• J. Am. Chem. Soc. 2011, 133, 7897–7908. Reaction Pathways of Proton Transfer in Hydrogen-Bonded Phenol-Carboxylate Complexes Explored by Combined UV-Vis and NMR Spectroscopy
  B. Koeppe, P. M. Tolstoy, H. H. Limbach
  
• Phys. Chem. A , 2011, 115, 9828-9836. NMR Study of Conformational Exchange and Geometries of Intramolecular Hydrogen Bonds in Monoanions of Succinic Acid and Derivatives
  J. Guo, P. M. Tolstoy, B. Koeppe, G. S. Denisov, H. H. Limbach, J.
  
• Two-dimensional UV-Vis/NMR Correlational Spectroscopy: A Heterospectral Signal Assignment of Hydrogen-Bonded Complexes, J. Phys. Chem. Lett., 2011, 2, 1106-1110
  B. Koeppe, P.M. Tolstoy, E. T. J. Nibbering, T. Elsaesser