Organic–Inorganic Hybrid Heterometallic Halides with Low-Dimensional Structures and Red Photoluminescence Emissions

Abstract

In recent years, although low-dimensional hybrid lead halides have received great attention due to the fascinating photoluminescent (PL) properties, the research is still on the early stage and only limited phases have been explored and characterized. Here, by introducing heterometals as mixed structural compositions and optical activity centers, we prepared a series of low-dimensional hybrid heterometallic halides, namely as, [(Me)-DABCO]2Cu2PbI6, [(Me)2-DABCO]2M5Pb2I13 (M = Cu and Ag) and [(Me)2-DABCO]­Ag2PbBr6 (Me = methyl group, DABCO = 1,4-diazabicyclo[2.2.2]­octane). These hybrid halides feature a low-dimensional 0D [Cu2PbI6]2– cluster, a 1D [M5Pb2I13]4– chain, and a 2D [Ag2PbBr6]2– layer, respectively, on the basis of corner-, edge- and face-sharing connecting of [MX4] tetrahedrons, [PbX5] quadrangular pyramids, and [PbX6] octahedrons. Under the photoexcitation, these hybrid heterometallic halides exhibit deep-red luminescent emissions from 711 to 801 nm with the largest Stocks shift of 395 nm. The temperature-dependent PL emissions, PL lifetime, and theoretical calculations are also investigated to probe into the intrinsic nature of photoluminescent emissions. This work affords new types of hybrid halides by introducing different metal centers to probe into the structural evolution and photoluminescent properties.

Zero‐Dimensional Hybrid Cd‐Based Perovskites with Broadband Bluish White‐Light Emissions

“…where I PL is the emission intensity at different temperature (T), I 0 is the emission intensity at 80 K, E a belongs to the activation energy related to the thermally activated non‐radiation process, and k B represents the Boltzmann constant (Figure a and 6b). The theoretical fittings give the activation energies E a of 72±7.062 meV and 56±6.181 meV for compounds 1 and 2 , respectively, which are close to those of hybrid metal halides (R) 2 CdBr 4 ⋅ DMSO (R=C 6 (CH 3 ) 5 CH 2 N(CH 3 ) 3 , 48 meV), (C 4 H 14 N 2 ) 2 In 2 Br 10 (61.8 meV), [(Me)‐DABCO] 2 Cu 2 PbI 6 (73 meV), etc …”

Ultra-Broad-Band-Excitable Cu(I)-Based Organometallic Halide with Near-Unity Emission for Light-Emitting Diode Applications

“…Due to the advantages of earth abundance, low toxicity, and low cost, copper (Cu)-based functional material has become a suitable choice to form Cu­(I)-based metal halides. , Recently, Hosono and co-workers first reported Cs 3 Cu 2 I 5 with efficient blue emission, which triggered the exploration of Cu­(I)-based metal halide luminescence materials . However, despite highly efficient blue/green emission, the suboptimal excitation peak position (∼300 nm) of the reported all-inorganic Cu + -based metal halides greatly restricted their further commercial applications. − Besides, organic–inorganic hybrid metal halides are an interesting family of functional materials with impressive structural diversity and enormous application prospects. ,, Unlike inorganic solids, the organic–inorganic hybrid metal halides allow us to artificially design the connectivity of an inorganic lattice by choosing suitable organic components. − For example, Li et al reported a lead-free Cu­(I)-based organic–inorganic perovskite-related material [K­(C 8 H 16 O 4 ) 2 ] 2 [Cu 4 I 6 ] with one-dimensional (1D) clusters, which exhibits greenish-yellow emission (545 nm) with a near-unity PLQY (∼97.8%) . However, the photoluminescence excitation (PLE) spectrum shows that blue light is still not located in the optimal excitation region.…”

Luminescent Thermochromism and White-Light Emission of a 3D [Ag4Br6] Cluster-Based Coordination Framework with Both Adamantane-like Node and Linker

“…Metal halide-based complexes with diverse organic species usually exhibit distinct photophysical properties and have extensive applications in optical devices, sensors, and white-light-emitting materials. − Thus, the luminescent emission band for 1 was performed. Upon UV-light irradiation (λ ex = 300 nm), the solid displayed a broad and weak emission band with a peak of 660 nm at ambient temperature.…”