Conformational Effect of Catechol-Terephthalonitrile Emitters Leading to Ambient Violet Phosphorescence

Organic ambient violet phosphorescent (AVP) materials are of great interest due to their involvement of high energy and longer-lived triplet excitons. Here, we show three fused ring functionalized donor–acceptor–donor (D–A–D/D–A–D′) emitters (BPT1–BPT3), in which two catechol-based donors (3,4-dihydroxybenzophenone, catechol, or 3,5-ditert-butylcatechol) are covalently fused to the terephthalonitrile acceptor via four O–C single bonds. Spectroscopic analysis revealed that all the molecules show AVP (∼390–394 nm, τAVP = 73–101 μs) with phosphorescence quantum yields (ϕP) of 1.8–27.4% due to low singlet–triplet gaps (0.036–0.046 eV) and conformational effects. BPT3 with bulky tert-butyl groups increases AVP (ϕP = 27.4%). Quantum chemistry calculations reveal flat (F1) and twisted (F2) conformers (ground state) with a low energy difference (∼4–5 kcal/mol) for all molecules; the F1 conformer is responsible for efficient AVP, while weak blue thermally activated delayed fluorescence with longer-lived delayed components is realized from the F2 conformer. This approach may provide important clues for the design of high-energy organic phosphorescent materials