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

Autori
Milašinović, Valentina ; Molčanov, Krešimir ; Krawczuk, Anna ; Bogdanov, Nikita ; Zakharov, Boris ; Boldyreva, Elena ; Jelsch, Christian ; Kojić-Prodić, Biserka

Izvornik
IUCrJ (2052-2525) 8 (2021), 4; 644-654

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

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

Sažetak
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 π-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.

Izvorni jezik
Hrvatski

Znanstvena područja
Kemija

POVEZANOST RADA