Structural Properties of Nickel Dimethylglyoxime at High Pressure: Single-Crystal X-Ray Diffraction and DFT Studies | Sciact - CRIS-system of Boreskov Institute of Catalysis

Structural Properties of Nickel Dimethylglyoxime at High Pressure: Single-Crystal X-Ray Diffraction and DFT Studies Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2014, Volume: 118, Number: 42, Pages: 24705-24713 Pages count : 9 DOI: 10.1021/jp508939g

Tags

DFT study, High pressure, Nickel dimethylglyoxime, Single crystal x-ray diffraction

Authors

Bruce-Smith I.F. ^1,2 , Zakharov B.A. ^1,3 , Stare J. ⁴ , Boldyreva E.V. ^1,3 , Pulham C.R. ²

Affiliations

1	Novosibirsk State University, Pirogova Str. 2, Novosibirsk, Russian Federation
2	School of Chemistry, Centre for Science at Extreme Conditions, University of Edinburgh, West Mains Road, Edinburgh, United Kingdom
3	Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Kutateladze Str. 18, Novosibirsk, Russian Federation
4	National Institute of Chemistry, Hajdrihova 19, Ljubljana, Slovenia

Structural changes in nickel dimethylglyoxime (Ni(dmg)2) were followed by single-crystal X-ray diffraction in a diamond-anvil cell (DAC) at pressures up to 5.1 GPa, that is, in the pressure range through the major color change point (2 GPa), but before the phase transition at 7.4 GPa. Significant average compression (∼4%/GPa) was observed, with anisotropic, but continuous and monotonic lattice strain. The maximum compression was observed for the direction perpendicular to planar layers of Ni(dmg)2 and thus corresponds to decreasing the shortest contacts between nickel cations. Compression within the layers was not so pronounced as the compression between the layers. The structure and dynamics of the short O-H···O hydrogen bond connecting the adjacent dimethylglyoxime ligands were investigated by periodic DFT calculations and showed evidence of a flat, asymmetric single-well proton potential facilitating large-amplitude proton oscillations. The proton motion appears to be coupled to the dynamics of the adjacent methyl groups, resulting in the increased asymmetry of the hydrogen bond at higher pressures.

Bruce-Smith I.F. , Zakharov B.A. , Stare J. , Boldyreva E.V. , Pulham C.R.
Structural Properties of Nickel Dimethylglyoxime at High Pressure: Single-Crystal X-Ray Diffraction and DFT Studies
The Journal of Physical Chemistry C. 2014. V.118. N42. P.24705-24713. DOI: 10.1021/jp508939g WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Sep 4, 2014
Accepted:	Sep 26, 2014
Published online:	Oct 14, 2014
Published print:	Oct 23, 2014

Web of science:	WOS:000343740300054
Scopus:	2-s2.0-84908108480
Elibrary:	23994942
Chemical Abstracts:	2014:1641872
Chemical Abstracts (print):	161:619182
OpenAlex:	W1530585094

DB	Citing
Web of science	22
Scopus	23
OpenAlex	24