2-Chloromalonaldehyde, a model system of resonance-assisted hydrogen bonding: vibrational investigation
| Autor: | Claudine Crépin, Justinas Ceponkus, Rasa Platakyte, Michèle Chevalier, Alejandro Gutiérrez-Quintanilla, G. Rojas-Lorenzo |
|---|---|
| Přispěvatelé: | Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Instituto Superior de Tecnologias y Ciencias Aplicadas - InSTEC (CUBA), SYSIPHE, Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11) |
| Rok vydání: | 2018 |
| Předmět: |
Materials science
Hydrogen bond General Physics and Astronomy chemistry.chemical_element 02 engineering and technology Resonance-assisted hydrogen bond 010402 general chemistry 021001 nanoscience & nanotechnology Resonance (chemistry) 01 natural sciences Enol 3. Good health 0104 chemical sciences Neon chemistry.chemical_compound symbols.namesake chemistry symbols Molecule Physical chemistry [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] Physical and Theoretical Chemistry 0210 nano-technology Raman spectroscopy Conformational isomerism |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2018, 20 (18), pp.12888-12897. ⟨10.1039/C7CP06481K⟩ |
| ISSN: | 1463-9084 1463-9076 |
| Popis: | International audience; The chelated enol isomer of 2-chloromalonaldehyde (2-ClMA) is experimentally characterized for the first time by IR and Raman spectroscopies. The spectra are obtained by trapping the molecule in cryogenic matrices and analyzed with the assistance of theoretical calculations. Experiments were performed in argon, neon and para-hydrogen matrices. The results highlight puzzling matrix effects, beyond site effects, which are interpreted as due to a tunneling splitting of the vibrational levels related to the proton transfer along the internal hydrogen bond (IHB). 2-ClMA is thus one of the very few molecules in which the H tunneling has been observed in cryogenic matrices. The comparison with its parent molecule (malonaldehyde) shows experimentally and theoretically the weakening of the IHB upon chlorination, with a reduced cooperative effect in the resonance assisted hydrogen bond. In addition, the Cl substitution induces an important stabilization of two open enol conformers. These two open forms appear in the spectra of as-deposited samples, meaning that, in contrast with other well-studied molecules of the same family (b-dialdehydes and b-diketones), they are present in the gas phase at room temperature. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|