Crystallization induced room-temperature phosphorescence and chiral photoluminescence properties of phosphoramides. Issue 20 (3rd May 2022)

• Record Type: Journal Article
• Authors: Jena, Satyam; Eyyathiyil, Jusaina; Behera, Santosh Kumar; Kitahara, Maho; Imai, Yoshitane; Thilagar, Pakkirisamy
• Is Part Of: Chemical science. Volume 13:Issue 20(2022)
• Page Start: 5893
• Page End: 5901
• Publication Date: 2022-05-03
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc00990k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The crystallization-induced room temperature phosphorescence and CPL of phosphoramides are reported. The nonplanar phenothiazine and the tetrahedral geometry of phosphorus curbed the non-radiative deactivation pathways, which led to improved RTP. Abstract : We report the design and synthesis of a series of room temperature phosphorescent phosphoramides TPTZPO, TPTZPS, and TPTZPSe with a donor (phenothiazine)–acceptor (P = X, X = O, S, and Se) architecture. All the compounds show structureless fluorescence with a nanosecond lifetime in dilute solutions. However, these compounds show dual fluorescence and room temperature phosphorescence (RTP) in the solid state. Both the intensity and energy of luminescence depend on the heteroatom attached to the phosphorus center. For example, compound TPTZPO with the PO unit exhibits fluorescence at a higher energy region than TPTZPS and TPTZPSe with the PS and PSe groups, respectively. Crystalline samples of TPTZPO, TPTZPS, and TPTZPSe show stronger RTP than the amorphous powder of respective compounds. Detailed steady-state, time-resolved photoluminescence and computational studies established that the 3 n–π* state dominated by the phenothiazine moiety is the emissive state of these compounds. Although TPTZPS and TPTZPSe crystallized in the chiral space group, only TPTZPSe showed chiroptical properties in the solid state. The luminescence dissymmetry factor ( g lum ) value of TPTZPS is small and below the detection limit, and a CPL spectrum could not be observed for this compound.