Shining Light on Inverted Singlet–Triplet Emitters

• Published in: Journal of chemical theory and computation 2024-01, Vol.20 (2), p.902-913
• Main Authors: Bedogni, Matteo, Giavazzi, Davide, Di Maiolo, Francesco, Painelli, Anna
• Format: Article
• Language: English
• Subjects: Spectroscopy and Excited States
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.3c01112

The inversion of the lowest singlet and triplet excited states, observed in several triangle-shaped organic molecules containing conjugated carbon and nitrogen atoms, is an astonishing result that implies the breakdown of Hund’s rule. The phenomenon attracted interest for its potential toward triplet harvesting in organic LEDs. On a more fundamental vein, the singlet–triplet (ST) inversion sheds new light on the role of electron correlations in the excited-state landscape of π-conjugated molecules. Relying on the celebrated Pariser–Parr–Pople model, the simplest model for correlated electrons in π-conjugated systems, we demonstrate that the ST inversion does not require triangle-shaped molecules nor any specific molecular symmetry. Indeed, the ST inversion does not require strictly non-overlapping HOMO and LUMO orbitals but rather a small gap and a small exchange integral between the frontier orbitals.