Altering central atoms and bromination sites of phosphorescence units to control ultralong organic room temperature phosphorescence

We report two strategies to expand the library of Phosphorescence Units, including altering the central atom and bromination. Directed by these two strategies, numerous new Phosphorescence Units can be designed. Due to the limitation of organic synthesis and commercial availability, eight organic units (BCz, NBF, BNT, BrBCz-1, BrBCz2, BrBCz-3, BrBCz-4 and BrBNT) were obtained to verify our proposed methods and study the impact of central atoms and bromination sites on organic room temperature phosphorescence. Considering BCz, NBF and BNT (Group I) together, when the central atom is N or S, the room temperature phosphorescence is on as BCz and BNT have higher ISC (Intersystem Crossing) efficiency than NBF; from N to S, phosphorescence wavelength red shifts because the T1 energy level is closely related to the central atom and the lifetime shortens due to different ISC efficiency. Considering BCz, BrBCz-1, BrBCz-2 and BrBCz-3 (Group II), bromination and different bromination sites on the benzene ring matters much to ISC efficiency but little to the intrinsic T1 energy level, leading to dramatical increase of phosphorescence intensity, sharp drop of phosphorescence lifetime and subtle change of phosphorescence wavelength (color). Considering BrBCz-4 and BrBNT (Group III), bromination on the naphthalene moiety greatly affects both ISC efficiency and the intrinsic T1 energy level, resulting in dramatical increase of phosphorescence intensity, sharp drop of phosphorescence lifetime and significant red shift of phosphorescence color. Therefore, BNT, BrBCz-1, BrBCz-2, BrBCz-3, BrBCz-4 and BrBNT can be regarded as new Phosphorescence Units while NBF cannot be. To our best knowledge, this work for the first time gives design suggestions of organic room temperature materials from the atomic level. This work may give a deep insight into organic phosphorescence from the perspective of Phosphorescence Units and lay foundation for their future applications.