Transforming Thermally Activated Delayed Fluorescence to Room-Temperature Phosphorescence through Modulation of the Donor in Charge-Transfer Cocrystals.

A cocrystallization strategy is used through incorporation of 1,2,4,5-tetracyanobenzene (TCNB) as an acceptor with halogen-substituent thioxanthone (TX) derivatives as donors. The resulting cocrystals TT-R (R = H, F, Cl, Br, or I) transform the thermally activated delayed fluorescence emission in the TT-H, TT-F, and TT-Cl cocrystals to room-temperature phosphorescence in the TT-Br and TT-I cocrystals. Definite crystal packing structures demonstrate a 1:1 alternative donor-acceptor stacking in the TT-H cocrystal, a 2:1 alternative donor-acceptor stacking in the TT-F and TT-Cl cocrystals, and a separate stacking of donor and acceptor in the TT-Br and TT-I cocrystals. A transformation law can be revealed that with an increase in atomic number from H, F, Cl, Br, to I, the cocrystals show the structural transformation of the number of aggregated TX-R molecules from monomers to dimers and finally to multimers. This work will facilitate an understanding of the effect of halogen substituents on the crystal packing structure and luminescence properties in the cocrystals.

A functional unit combination strategy for enhancing red room-temperature phosphorescence.

Red room-temperature phosphorescence (RTP) materials based on non-metallic organic compounds are less reported compared to the commonly found green RTP materials. Here, we propose a novel approach to obtain red RTP materials by integrating and combining two functional units, resembling a jigsaw puzzle. In this approach, benzo[c][2,1,3]thiadiazole (BZT) serves as the red RTP unit, while a folding unit containing sulphur/oxygen is responsible for enhancing spin-orbit coupling (SOC) to accelerate the intersystem crossing (ISC) process. Three new molecules (SS-BZT, SO-BZT, and OO-BZT) were designed and synthesized, among which SS-BZT and SO-BZT with folded geometries demonstrate enhanced red RTP in their monodisperse films compared to the parent BZT. Meanwhile, the SS-BZT film shows a dual emission consisting of blue fluorescence and red RTP, with a significant spectral separation of approximately 150 nm, which makes the SS-BZT film highly suitable for applications in optical oxygen sensing and ratiometric detection. Within the oxygen concentration range of 0-1.31%, the SS-BZT film demonstrates a quenching constant of 2.66 kPa-1 and a quenching efficiency of 94.24%, indicating that this probe has the potential to accurately detect oxygen in a hypoxic environment.