Gurinov Andrei A, Denisov Gleb S, Borissova Alexandra O, Goloveshkin Alexander S, Greindl Julian, Limbach Hans-Heinrich, Shenderovich Ilya G
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.
J Phys Chem A. 2017 Nov 16;121(45):8697-8705. doi: 10.1021/acs.jpca.7b09285. Epub 2017 Nov 7.
Hydrogen bond geometries in the proton-bound homodimers of quinoline and acridine derivatives in an aprotic polar solution have been experimentally studied using 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.
在非质子极性溶液中，喹啉和吖啶衍生物的质子键合同二聚体中的氢键几何结构已在120K下通过核磁共振氢谱进行了实验研究。报道的结果表明，介质介电常数的增加会导致N···N距离的缩短。缩短程度取决于同二聚体的大小及其取代基特异性溶剂化特征。使用计算研究中采用的传统隐式溶剂模型无法重现这些效应中的任何一种。一般来说，吡啶、喹啉和吖啶衍生物同二聚体中的N···N距离按气相>固态>极性溶剂的顺序减小。
