Achieving TADF and RTP with Stimulus‐Responsiveness and Tunability from Phenothiazine‐Based Donor−Acceptor Molecules

Abstract Research of thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP) materials is attractive owing to their extensive applications in various fields. However, achieving organic TADF and RTP materials, particularly those with stimulus‐responsiveness and tunability, is highly desirable but challenging and rarely reported. Herein, two easily synthesized organic molecules are reported with abnormal stimulus‐responsive switchable TADF and RTP effects, in which phenothiazine (PTZ) and benzo[b]phenothiazine (BPTZ) based donor−acceptor molecules PTZ‐DBQ and BPTZ‐DBQ show mechanical‐induced TADF in crystalline phase and photo‐responsive RTP in doping poly(methyl methacrylate) (PMMA) films. This is the first time tetracyclic BPTZ has been used as a donor in achieving TADF and RTP materials, and it is found that BPTZ‐DBQ exhibits remarkably better photophysical properties than PTZ‐DBQ. Systematic studies of experimental results and theoretical calculations indicate that the conformational heterogeneity plays an essential role in achieving mechanical‐induced TADF with mechanochromic luminescence (MCL) property. Embedding the organic phosphors into rigid polymer matrices effectively suppresses the molecular motion, thus turning on the RTP emission channel. The conversion of 3 O 2 to 1 O 2 under UV irradiation is mainly responsible for the photo‐induced process. These multifunctional luminescent materials have great potential applications in chemical sensors, information encryption, and anti‐counterfeiting.