NMR Study of Solvation Effect on the Geometry of Proton-Bound Homodimers of Increasing Size.

Autor: Gurinov AA; Institute of Chemistry and Biochemistry, Free University Berlin , Takustrasse 3, 14195 Berlin, Germany.; The Imaging and Characterization Core Lab, King Abdullah University of Science and Technology , Al-Khawarizimi Building 01, Thuwal 23955-6900, Saudi Arabia., Denisov GS; Institute of Physics, St. Petersburg State University , Ulyanovskaya str. 1, 198504 St. Petersburg, Russian Federation., Borissova AO; A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 119991, Vavilov Str., 28, Moscow, Russia., Goloveshkin AS; A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 119991, Vavilov Str., 28, Moscow, Russia., Greindl J; Institute of Organic Chemistry, University of Regensburg , Universitaetstrasse 31, 93053 Regensburg, Germany., Limbach HH; Institute of Chemistry and Biochemistry, Free University Berlin , Takustrasse 3, 14195 Berlin, Germany., Shenderovich IG; Institute of Chemistry and Biochemistry, Free University Berlin , Takustrasse 3, 14195 Berlin, Germany.; Institute of Organic Chemistry, University of Regensburg , Universitaetstrasse 31, 93053 Regensburg, Germany.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. A [J Phys Chem A] 2017 Nov 16; Vol. 121 (45), pp. 8697-8705. Date of Electronic Publication: 2017 Nov 07.
DOI: 10.1021/acs.jpca.7b09285
Abstrakt: Hydrogen bond geometries in the proton-bound homodimers of quinoline and acridine derivatives in an aprotic polar solution have been experimentally studied using 1 H NMR at 120 K. The reported results show that an increase of the dielectric permittivity of the medium results in contraction of the N···N distance. The degree of contraction depends on the homodimer's size and its substituent-specific solvation features. Neither of these effects can be reproduced using conventional implicit solvent models employed in computational studies. In general, the N···N distance in the homodimers of pyridine, quinoline, and acridine derivatives decreases in the sequence gas phase > solid state > polar solvent.
Databáze: MEDLINE
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