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Zero-dimensional (0D) hybrid metal halides have been emerged as room-temperature phosphorescence (RTP) materials, but synchronous optimization of multiple phosphorescence performance in one structural platform remains less resolved, and stable RTP activity in aqueous medium is also unrealized due to serious instability toward water and oxygen. Herein, we demonstrated a photophysical tuning strategy in a new 0D hybrid zinc halide family of (BTPP)2ZnX4 (BTPP = benzyltriphenylphosphonium, X = Cl and Br). Infrequently, the delicate combination of organic and inorganic species enables this family to display multiple ultralong green afterglow and efficient self-trapped exciton (STE) associated cyan phosphorescence. Compared with inert luminescence of [BTPP]+ cation, incorporation of anionic [ZnX4]2- effectively enhance the spin-orbit coupling effect, which significantly boosts the photoluminescence quantum yield (PLQY) up to 30.66% and 54.62% for afterglow and phosphorescence, respectively. Synchronously, the corresponding luminescence lifetime extend to 143.94 ms and 0.308 μs surpassing the indiscernible phosphorescence of [BTPP]X salt. More importantly, this halide family presents robust RTP emission with nearly unattenuated PLQY in water and harsh condition (acid and basic aqueous solution) over half a year. The highly efficient integrated afterglow and STE phosphorescence as well as ultrahigh aqueous state RTP realize multiple anti-counterfeiting applications in wide chemical environments., (© 2024 Wiley‐VCH GmbH.)

Recently, zero-dimensional (0D) hybrid metal halides have attracted intensive attention with wide applications in solid-state lighting and display diodes. Herein, by using a facile wet-chemistry method, we prepared one new 0D hybrid antimony halide of [HMHQ] 2 SbCl 5  ⋅ 2H 2 O (MHQ=2-methyl-8-hydroxyquinoline) based on the discrete [SbCl 5 ] 2- unit. Remarkably, the bulk crystals of [HMHQ] 2 SbCl 5  ⋅ 2H 2 O exhibit strong cyan light emission with a promising photoluminescence quantum yield (PLQY) of 18.92%. Systematical studies disclose that the cyan emission is mainly derived from the radiative recombination within conjugated organic cation. Benefiting from the promising luminescent performance, this 0D antimony halide can be utilized as an excellent down-conversion light emitting luminescent material to assemble white light-emitting diodes with high color rendering index (CRI) of 90.2., (© 2022 Wiley-VCH GmbH.)

A convenient and rapid detection method for methanol in ethanol remains a major challenge due to their indistinguishable physical properties. Herein, a novel fluorescence probe based on perovskite was successfully designed to overcome this bottleneck. We report a new zero-dimensional (0D) hybrid perovskite of [MP] 2 In x Sb 1-x Cl 7  ⋅ 6 H 2 O (MP=2-methylpiperazine) displaying an unusual green light emission with near-unity photoluminescence quantum yield. Remarkably, this 0D perovskite exhibits reversible methanol-response luminescence switching between green and yellow color but fail in any other organic vapors. Even for blended alcohol solutions, the luminescent probe exhibits excellent sensing performance with multiple superiorities of rapid response time (30 s) and ultra-low detection limit (40 ppm), etc. Therefore, this 0D perovskite can be utilized as a perfect fluorescence probe to detect traces of methanol from ethanol with ultrahigh sensitivity, selectivity and repeatability. To the best of our knowledge, this work represents the first perovskite as fluorescence probe for methanol with wide potential in environmental monitoring and methanol detection, etc., (© 2022 Wiley-VCH GmbH.)

Mn 2+ doped colloidal three-dimensional (3D) lead halide perovskite nanocrystal (PNC) has attracted intensive research attention; however, the low exciton binding energy and fatal optical instability of 3D PNC seriously hinder the optoelectronic application. Therefore, it remains significant to explore new stable host perovskite with strongly bound exciton to realize more desirable luminescent property. In this work, we utilized bulk one-dimensional (1D) hybrid perovskite of [AEP]PbBr 5  ⋅ H 2 O (AEP=N-aminoethylpiperazine) as structural platform to rationally optimize the luminescent property by a controllable Mn 2+ doping strategy. Significantly, the series of Mn 2+ -doped 1D [AEP]PbBr 5  ⋅ H 2 O show enhanced energy transfer efficiency from the strongly bound excitons of host material to 3d electrons of Mn 2+ ions, resulting in tunable broadband light emissions from weak yellow to strong red spectral range with highest photoluminescence quantum yield up to 28.41 %. More importantly, these Mn 2+ -doped 1D perovskites display ultrahigh structural and optical stabilities in humid atmosphere, water and high temperature exceeding the conventional 3D PNC. Combined highly efficient, tunable and stable broadband light emissions enable Mn 2+ -doped 1D perovskite as excellent down-converting phosphor showcasing the potential application in white light emitting diode. This work not only provides a profound understanding of low-dimensional perovskites but also opens a new way to rationally design high-performance broadband light emitting perovskites for solid-state lighting and displaying devices., (© 2021 Wiley-VCH GmbH.)

Metal trimers [M 3 (O/OH)](OOCR) 6 are among the most important structural building blocks. From these trimers, a great success has been achieved in the design of 6- or 9-connected framework materials with various topological features and outstanding gas-sorption properties. In comparison, 8-connected trimer-based metal-organic frameworks (MOFs) are rare. Given multiple competitive pathways for the formation of 6- or 9-connected frameworks, it remains challenging to identify synthetic or structural parameters that can be used to direct the self-assembly process toward trimer-based 8-connected materials. Here, a viable strategy called angle bending modulation is revealed for creating a prototypical MOF type based on 8-connected M 3 (OH)(OOCR) 5 (Py-R) 3 trimers (M = Zn, Co, Fe). As a proof of concept, six members in this family are synthesized using three types of ligands (CPM-80, -81, and -82). These materials do not possess open-metal sites and show excellent uptake capacity for various hydrocarbon gas molecules and inverse C 2 H 6 /C 2 H 4 selectivity. CPM-81-Co, made from 2,5-furandicarboxylate and isonicotinate, features selectivity of 1.80 with high uptake capacity for ethane (123 cm 3 g -1 ) and ethylene (113 cm 3 g -1 ) at 298 K and 1 bar., (© 2020 Wiley-VCH GmbH.)

Recently, low-dimensional organic-inorganic hybrid metal halide perovskites acting as single-component white-light emitting materials have attracted extensive attention, but most studies concentrate on hybrid lead perovskites. Herein, we present two isomorphic zero-dimensional (0D) hybrid cadmium perovskites, (HMEDA)CdX 4 (HMEDA=hexamethylenediamine, X=Cl (1), Br (2)), which contain isolated [CdX 4 ] 2- anions separated by [HMEDA] 2+ cations. Under UV light excitation, both compounds display broadband bluish white-light emission (515 nm for 1 and 445 nm for 2) covering the entire visible light spectrum with sufficient photophysical stabilities. Remarkably, compound 2 shows a high color rendering index (CRI) of 83 enabling it as a promising candidate for single-component WLED applications. Based on the temperature-dependent, powder-dependent and time-resolved PL measurements as well as other detailed studies, the broadband light emissions are attributed to self-trapped excitons stemming from the strong electron-phonon coupling., (© 2020 Wiley-VCH GmbH.)

Considering the instability and low photoluminescence quantum yield (PLQY) of blue-emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d 10 transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH 4 ) 2 ]CuPbBr 5 with new type of three-dimensional (3D) anionic framework. [(NH 4 ) 2 ]CuPbBr 5 exhibits strong band-edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH 4 ) 2 ]CuPbBr 5 also displays broadband red light emissions derived from self-trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non-perovskite bimetallic halide with highly efficient and stable blue light emission., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Recently, 2D organic-inorganic hybrid lead halide perovskites have attracted intensive attention in solid-state luminescence fields such as single-component white-light emitters, and rational optimization of the photoluminescence (PL) performance through accurate structural-design strategies is still significant. Herein, by carefully choosing homologous aliphatic amines as templates, isotypical perovskites [DMEDA]PbCl 4 (1, DMEDA=N,N-dimethylethylenediamine) and [DMPDA]PbCl 4 (2, DMPDA=N,N-dimethyl-1,3-diaminopropane) having tunable and stable broadband bluish white emission properties were rationally designed. The subtle regulation of organic cations leads to a higher degree of distortion of the 2D [PbCl 4 ] 2- layers and enhanced photoluminescence quantum efficiencies (<1 % for 1 and 4.9 % for 2). The broadband light emissions could be ascribed to self-trapped excitons on the basis of structural characterization, time-resolved PL, temperature-dependent PL emission, and theoretical calculations. This work gives a new guidance to rationally optimize the PL properties of low-dimensional halide perovskites and affords a platform to probe the structure-property relationship., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Visible light driven photocatalysts based on crystalline microporous metal halogenides received much less attention compared with dense or composite oxide semiconductors. Using the well-known photosensitive transition metal-complexes [TM(2,2-bipy) 3 ] 2+ (TM=Fe, Co, Ni, Ru) as templates, a special three-dimensional (3D) metal halogenide framework of [TM(2,2-bipy) 3 ]Cu 4 Br 6 was designed with [Cu 4 Br 4 ] cluster as 4-connected node. These microporous materials feature narrow band gaps and stable visible light driven photocatalytic properties including water reduction to provide H 2 and photodegradation of organic pollutants. The study of electronic band structure shows that the TM complexes effectively prevent the recombination of photo-induced electron/hole pairs leading to excellent photocatalytic activity and photochemical stability. This work represents the first 3D microporous metal halogenides used as visible light driven photocatalyst to provide hydrogen energy., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Four new quaternary chalcogenides, Ba4AgGaS6 (1), Ba4AgGaSe6 (2), Ba4CuInS6 (3), and Ba4AgInS6 (4), were synthesized by solid-state reactions and their structures were characterized through single-crystal X-ray diffraction. In spite of their similar chemical compositions, the flexible arrangement between the transition metals and the triel atoms leads to subtle differences in their polyanion structures. All structures feature similar [MTrQ6](8-) 1D polyanionic chains (M=Cu, Ag; Tr=Ga, In; Q=S, Se), which are constructed from corner-sharing MQ4 or TrQ4 tetrahedra. However, the transition metals and triels are mixed in 1, 2, and 3, but they occupy independent crystallographic sites in 4. As a result, compounds 1-3 belong to the known Ba2CoS3 (Pnma No. 62) or Ba2 MnS3 (Pnma No. 62) class, whereas 4 crystallizes in its own structural type within the monoclinic P2₁/c (No. 14) space group. The structural relationship among these new phases was also studied with the aid of DFT calculations and related optical properties are presented as well., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)