Hybrid Metal Halides with Multiple Photoluminescence Centers

• Published in: Angewandte Chemie International Edition Vol. 58; no. 51; pp. 18670 - 18675
• Main Authors: Li, Mingze, Zhou, Jun, Zhou, Guojun, Molokeev, Maxim S., Zhao, Jing, Morad, Viktoriia, Kovalenko, Maksym V., Xia, Zhiguo
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 16.12.2019
• Edition: International ed. in English
• Subjects: 0D materials; Anions; Clusters; Durability; Excitons; Facilities management; Halides; Lead compounds; light-emitting diodes; Luminescence; manganese; Manganese ions; Metal halides; Metals; Optical properties; Organic light emitting diodes; Photoluminescence; Photons; Polyhedra; White light; metal halides; photoluminescence; light-emitting diodes; 0D materials; manganese
• DOI: 10.1002/anie.201911419
• ISSN: 1433-7851

Very little is known about the realm of solid‐state metal halide compounds comprising two or more halometalate anions. Such compounds would be of great interest if their optical and electronic properties could be rationally designed. Herein, we report a new example of metal halide cluster‐assembled compound (C9NH20)9[Pb3Br11](MnBr4)2, featuring distinctly different anionic polyhedra, namely, a rare lead halide cluster [Pb3Br11]5− and [MnBr4]2−. In accordance with its multinary zero‐dimensional (0D) structure, this compound is found to contain two distinct emission centers, 565 nm and 528 nm, resulting from the formation of self‐trapped excitons and 4T1‐6A1 transition of Mn2+ ions, respectively. Based on the high durability of (C9NH20)9[Pb3Br11](MnBr4)2 upon light and heat, as well as high photoluminescence quantum yield (PLQY) of 49.8 % under 450 nm blue light excitation, white light‐emitting diodes (WLEDs) are fabricated, showcasing its potential in backlight application. Luminescent metal halide: A novel 0D metal halide material (C9NH20)9[Pb3Br11](MnBr4)2 has two distinct emitting centers, self‐trapped excitons (STE) residing on [Pb3Br11]5− clusters and 4T1‐to‐6A1 transitions of Mn2+ ions in [MnBr4]2− tetrahedral units. This is the first example of Mn2+ emission and STE emissioncoexisting in a single crystalline material and allows white light‐emitting diodes (WLEDs) to be fabricated.