Dual Monomeric Inorganic Units Constructed Bright Emissive Zero-Dimensional Antimony Chlorides with Solvent-Induced Reversible Structural Transition

Abstract

A 5 M 2 X 11 and A 3 M 2 X 9 families (A = monovalent organic cation; M = trivalent metal; X = halogen) are receiving increasing attention because of their combination of easy solution processability and superior ferroelectricity properties. However, synthesizing highly efficient A 5 M 2 X 11 and A 3 M 2 X 9 -type fluorophores with multiple monomeric inorganic units and achieving their structural interconversion remains challenging. Here, we report two novel zero-dimensional (0D) antimony halides, (C 10 H 16 N) 5 Sb 2 Cl 11 •C 2 H 3 N (1) and (C 10 H 16 N) 3 Sb 2 Cl 9 (2), which not only contain two distinct [SbX n ] 3−n units but also have excellent orange (590 nm) and yellow-green emission (540 nm) with high PLQY of 17.7% and 31.5%, respectively. Interestingly, a reversible structural conversion could be triggered by acetonitrile steam stimulation, accompanied by luminescence switching properties. This work not only enriches the structure of hybrid Sb-based halides but also provides the possibility of well-known A 5 M 2 X 11 and A 3 M 2 X 9 families as structural transformation materials.

Photoluminescence and Nonlinear Optical Properties of Two Terpyridine-Based Hybrid Zn/Cd Halides

“…After decades of development, PL materials with light emission extending from blue to the near-infrared region have been developed from LD HMHs . Some LD HMHs were even found to be with ultrabroadband emission in the visible range, providing chances to fabricate white light LEDs by single-phase white-emitting materials. − However, many of them contain toxic lead, which can be a health risk when used on a large scale. The pursuit of environmentally friendly, long-term stable, and high-efficiency light emitters has been continuing, promoting the continuous development of novel organo-ammonium as the cation of LD HMHs.…”

Antimony Doping Enabled Photoluminescence Quantum Yield Enhancement in 0D Inorganic Bismuth Halide Crystals

“…Among the metal halides with abundant configurations, zero-dimensional (0D) analogues received more attention, thanks to the distinctive soft lattices and intense electron–lattice interaction, accordingly facilitating the formation of STEs . Particularly, bismuth-based halides are suggested as promising matrices because of the good physicochemical stabilities and environmental friendliness.…”

Zero-dimensional antimony halides with tunable photoluminescence via halogen ligand modulation

“…With the emergence of plentiful hybrid antimony halides, the relationship between the composition, configuration and luminescence properties has gradually attracted increasing attention for the improvement of their overall photophysical performances. 22–28 Generally, the production of luminescence mainly depends on the coordination environment of antimony halides, whereas organic cations without fluorophores, although not decisive for emission properties, play an important regulatory role in achieving enhanced quantum yields and luminescence lifetimes by influencing weak inter- or intra-molecular interactions. 29–35 For instance, 0D (C 12 H 28 N)SbCl 4 (C 12 H 28 N + = tetrapropylammonium cation) with seesaw-shaped [SbCl 4 ] − complexes has been reported and proved to be not emissive at room temperature, while (C 12 H 28 N) 2 SbCl 5 with pyramid-shaped [SbCl 5 ] 2− species exhibited a near-unity quantum yield of 96.8%.…”