scholarly journals NMR Properties of the Cyanide Anion, a Quasisymmetric Two-Faced Hydrogen Bonding Acceptor

Symmetry ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1298
Author(s):  
Ilya G. Shenderovich ◽  
Gleb S. Denisov
Keyword(s):  
Hydrogen Bonding ◽  
Experimental Studies ◽  
Polarizable Continuum Model ◽  
Coupling Constants ◽  
Scalar Coupling ◽  
Cyanide Anion ◽  
Molecular Systems ◽  
Polarizable Continuum ◽  
Chemical Shieldings ◽  
Nmr Properties

The isotopically enriched cyanide anion, (13C≡15N)−, has a great potential as the NMR probe of non-covalent interactions. However, hydrogen cyanide is highly toxic and can decompose explosively. It is therefore desirable to be able to theoretically estimate any valuable results of certain experiments in advance in order to carry out experimental studies only for the most suitable molecular systems. We report the effect of hydrogen bonding on NMR properties of 15N≡13CH···X and 13C≡15NH···X hydrogen bonding complexes in solution, where X = 19F, 15N, and O=31P, calculated at the ωB97XD/def2tzvp and the polarizable continuum model (PCM) approximations. In many cases, the isotropic 13C and 15N chemical shieldings of the cyanide anion are not the most informative NMR properties of such complexes. Instead, the anisotropy of these chemical shieldings and the values of scalar coupling constants, including those across hydrogen bonds, can be used to characterize the geometry of such complexes in solids and solutions. 1J(15N13C) strongly correlates with the length of the N≡C bond.

Theoretical studies of the structural, electronic, and 19F NMR properties of linear and branched perfluorobutanesulfonate

2013 ◽  
Vol 91 (12) ◽  
pp. 1272-1280
Author(s):  
Xue Qin Ran ◽  
John D. Goddard
Keyword(s):  
Chemical Shifts ◽  
Polarizable Continuum Model ◽  
Coupling Constants ◽  
Basis Set ◽  
Structural And Electronic Properties ◽  
J Coupling ◽  
Fermi Contact ◽  
J Coupling Constants ◽  
Polarizable Continuum ◽  
Nmr Properties

The structural and electronic properties of linear and branched perfluorobutanesulfonate (PFBS) in its anionic, acidic, and potassium or sodium salt forms were studied in a polarizable continuum model (PCM) of methanol solvent with the B3LYP functional and the 6-31G(d,p) basis set. The 19F chemical shifts and 19F−19F J-coupling constants were determined in a PCM of methanol solvent with GIAO B3LYP/6-31++G(d,p). The differences in energy, enthalpy, and free energy of the four PFBS isomers were compared. The data indicate that the linear PFBS species is less stable than the branched isomers and the isomer with the tert-butyl-like structure is the most stable. The J-coupling contributions via both a non-Fermi contact mechanism and a long chain of bonds (through-bond) indicate that 19F−19F J-coupling constants are long range in these branched PFBS isomers. The calculated and experimental 19F chemical shifts for the linear PFBS species are in good agreement. In addition, the results obtained establish the similarities between the geometries and electronic and NMR properties of linear PFBS and linear perfluorooctanesulfonate (PFOS).

scholarly journals Theoretical Study of a New Diarylic Ligand for M2+ Cations Detection

Proceedings ◽  
2018 ◽  
Vol 9 (1) ◽  
pp. 45
Author(s):  
Carla M. Ormachea ◽  
Cristián A. Ferretti ◽  
Pablo Noriega ◽  
Leandro Gutierrez ◽  
Pedro M. E. Mancini ◽  
...  
Keyword(s):  
Density Functional ◽  
Theoretical Study ◽  
Polarizable Continuum Model ◽  
Ligand Complex ◽  
Hydrazone Ligand ◽  
Molecular Systems ◽  
The Density Functional Theory ◽  
Td Dft ◽  
Structural Electronics ◽  
Polarizable Continuum

A novel byphenyl hydrazone ligand developed as a chemosensor for the detection of Cu2+ was studied using a theoretical analysis based on the density functional theory (DFT) and time-dependent DFT (TD-DFT). The geometries of the ligand (L) and the Cu2+-ligand complex were optimized at the CAM-B3LYP/631+G(d,p) level of theory in dimethyl sulfoxide, using the conductor-like polarizable continuum model. The adsorption spectra of these molecular systems were analyzed and compared with the experimental data. Theoretical study of the structural, electronics and optical properties allowed us to understand the chemical changes that the ligand undergoes in the complexation process with the Cu+2 ion.

scholarly journals Hydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems

2019 ◽  
Vol 131 (49) ◽  
pp. 18027-18035 ◽  
Author(s):  
Alexander E. Khudozhitkov ◽  
Jan Neumann ◽  
Thomas Niemann ◽  
Dzmitry Zaitsau ◽  
Peter Stange ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Ionic Liquids ◽  
Coupling Constants ◽  
Salt Bridges ◽  
Molecular Systems ◽  
Quadrupole Coupling
Sign in / Sign up

Export Citation Format

Share Document