Details

Autor(en) / Beteiligte

• Förster, Christoph
• Osthues, Helena
• Schwab, Dominik
• Doltsinis, Nikos L.
• Heinze, Katja

Titel

Quantum Chemical Study of the Pressure‐dependent Phosphorescence of [Cr(ddpd)2]3+ in the Solid State

Ist Teil von

• Chemphyschem, 2023-06, Vol.24 (12), p.e202300165-n/a

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

Wiley-Blackwell subscription journals

Beschreibungen/Notizen

• The chromium(III) complex [Cr(ddpd)2][BF4]3 shows two spin‐flip emission bands in the near‐infrared spectral region. These bands shift bathochromically by −14.1 and −7.7 cm−1 kbar−1 under hydrostatic pressure (Angew. Chem. Int. Ed. 2018, 57, 11069). The present study elucidates the structural changes of the chromium(III) cations under pressure using density functional theory with periodic boundary conditions and the resulting effects on the excited state energies using high‐level CASSCF‐NEVPT2 calculations. The differences of the bands in pressure sensitivity are traced back to a different orbital occupation of the intraconfigurational excited states. The bathochromic shifts of the two spin‐flip emission bands of the molecular ruby [Cr(ddpd)2][BF4]3 under hydrostatic pressure are investigated using a combination of density functional theory with periodic boundary conditions for the geometries at different pressures and high‐level CASSCF‐NEVPT2 calculations for the relevant excited state energies explaining the unusually large pressure sensitivity of the molecular complex’ emission.