Switching Singlet Exciton to Triplet for Efficient Pure Organic Room-Temperature Phosphorescence by Rational Molecular Design

The design and regulation of phosphors are attractive but challenging because of the spin-forbidden intersystem crossing (ISC) process. Here, a new perspective on the enhancement of the ISC is proposed and demonstrated. Different from current strategies, the ISC yield (Φ_ISC) is enhanced by decreasing the fluorescence radiative transition rate constant (k_F) via rational molecular designing rather than boosting the spin-orbit coupling by decorating the molecular skeleton with a heavy atom, heteroatom, or carbonyl. The k_F of the designed molecule in this case is associated with the substituent position of the methoxy group, which alters the distribution of the front orbitals. The S₀ → S₁ transition of these compounds evolves from a bright state to a dark state gradually with the variation of the substituent position, accompanied by the decrease of k_F and increase of Φ_ISC. The fluorescence emission is switched to phosphorescence emission successfully by regulating the k_F. This work provides an alternative strategy to design efficient room-temperature phosphorescence material.