Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure

Valentina Milasinovic, Kresimir Molcanov, Anna Krawczuk, Nikita E. Bogdanov, Boris A. Zakharov, Elena Boldyreva, Christian Jelsch, Biserka Kojic-Prodic

Research output: Contribution to journalArticlepeer-review

Abstract

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 pi-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.

Original languageEnglish
Pages (from-to)644-654
Number of pages11
JournalIUCrJ
Volume8
Issue numberPt 4
DOIs
Publication statusPublished - Jul 2021

Keywords

  • pi-stacking
  • non-aromatic rings
  • multicentre bonding
  • charge density
  • high pressure
  • EXPERIMENTAL ELECTRON-DENSITY
  • DATA-BANK
  • SMALL-MOLECULE
  • WAVE-FUNCTIONS
  • PI-STACKING
  • REFINEMENT
  • CRYSTALS
  • QUALITY
  • TRANSFERABILITY
  • PARAMETERS

OECD FOS+WOS

  • 1.04 CHEMICAL SCIENCES
  • 2.05 MATERIALS ENGINEERING
  • 1.04.FI CRYSTALLOGRAPHY

Fingerprint

Dive into the research topics of 'Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure'. Together they form a unique fingerprint.

Cite this