New Light on an Old Story: Breaking Kasha’s Rule in Phosphorescence Mechanism of Organic Boron Compounds and Molecule Design

In this work, the phosphorescence mechanism of (E)-3-(((4-nitrophenyl)imino)methyl)-2H-thiochroman-4-olate-BF2 compound (S-BF2) is investigated theoretically. The phosphorescence of S-BF2 has been reassigned to the second triplet state ([Formula: see text]) by the density matrix renormalization group (DMRG) method combined with the multi-configurational pair density functional theory (MCPDFT) to approach the limit of theoretical accuracy. The calculated radiative and non-radiative rate constants support the breakdown of Kasha’s rule further. Our conclusion contradicts previous reports that phosphorescence comes from the first triplet state ([Formula: see text]). Based on the revised phosphorescence mechanism, we have purposefully designed some novel compounds in theory to enhance the phosphorescence efficiency from [Formula: see text] by replacing substitute groups in S-BF2. Overall, both S-BF2 and newly designed high-efficiency molecules exhibit anti-Kasha [Formula: see text] phosphorescence instead of the conventional [Formula: see text] emission. This work provides a useful guidance for future design of high-efficiency green-emitting phosphors.