Charge Density Studies of Multicentre Two-Electron Bonding of an Anion Radical at Non-Ambient Temperature and Pressure | Sciact - CRIS-system of Boreskov Institute of Catalysis

Charge Density Studies of Multicentre Two-Electron Bonding of an Anion Radical at Non-Ambient Temperature and Pressure Full article

Journal

IUCrJ
ISSN: 2052-2525

Output data

Year: 2021, Volume: 8, Number: 4, Pages: 644-654 Pages count : 11 DOI: 10.1107/S2052252521005273

Tags

π-stacking; non-aromatic rings; multicentre bonding; charge density; high pressure

Authors

Milašinović Valentina ¹ , Molčanov Krešimir ¹ , Krawczuk Anna ^2,3 , Bogdanov Nikita E. ^4,5 , Zakharov Boris A. ^4,5 , Boldyreva Elena V. ^4,5 , Jelsch Christian ⁶ , Kojić-Prodić Biserka ¹

Affiliations

1	Department of Physical Chemistry, Rudjer Bošković Institute, Bijenička 54, Zagreb 10000, Croatia
2	Institute of Inorganic Chemistry, University of Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany
3	Faculty of Chemistry, Jagiellonian University in Krakow, Gronostajowa 2, Krakow 30-387, Poland
4	Boreskov Institute of Catalysis, SB RAS, Lavrentiev Avenue 5, Novosibirsk 630090, Russian Federation
5	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russian Federation
6	CRM2, CNRS, UMR 7036, Université de Lorraine, BP 70239 Nancy, France

Funding (2)

1	Ministry of Science and Education of the Croatia	IP-2019-04-4674
2	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0002

The variation of charge density of two-electron multicentre bonding (pancake bonding) between semiquinone radicals with pressure and temperature was studied on a salt of 5,6-dichloro-2,3-dicyanosemiquinone radical anion (DDQ) with 4-cyano-N-methylpyridinium cation (4-CN) using the Transferable Aspheric Atom Model (TAAM) refinement. The pancake-bonded radical dimers are stacked by non-bonding -interactions. With rising pressure, the covalent character of interactions between radicals increases, and above 2.55 GPa, the electron density indicates multicentric covalent interactions throughout the stack. The experimental charge densities were verified and corroborated by periodic DFT computations. The TAAM approach has been tested and validated for atomic resolution data measured at ambient pressure; this work shows this approach can also be applied to diffraction data obtained at pressures up to several gigapascals.

Milašinović V. , Molčanov K. , Krawczuk A. , Bogdanov N.E. , Zakharov B.A. , Boldyreva E.V. , Jelsch C. , Kojić-Prodić B.
Charge Density Studies of Multicentre Two-Electron Bonding of an Anion Radical at Non-Ambient Temperature and Pressure

IUCrJ. 2021. V.8. N4. P.644-654. DOI: 10.1107/S2052252521005273 WOS Scopus AN PMID OpenAlex

Full text from publisher

Submitted:	Sep 30, 2020
Accepted:	May 25, 2021
Published online:	Jun 12, 2021
Published print:	Jul 1, 2021

Web of science:	WOS:000670812900015
Scopus:	2-s2.0-85130294988
Chemical Abstracts:	2021:1499531
PMID:	34258012
OpenAlex:	W3167289221

DB	Citing
Web of science	9
Scopus	10
OpenAlex	8