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The new two-dimensional coordination polymer, poly[(μ4-1-phenyl-1 H-1,2,3,4-tetrazole-5-thiolato)copper(I)], [Cu(C7H5N4S)] n, has been prepared under solvothermal conditions by reacting CuBr with 1-phenyl-1 H-1,2,3,4-tetrazole-5-thiol (Hptt) in an acetonitrile and acetone solution. In the crystal structure, each CuI ion is coordinated by two N atoms and two S atoms from four ptt− ligands, and each ptt− ligand links four CuI ions to form two-dimensional layers which lie parallel to the (100) plane. These layers stack along the [100] direction via van der Waals interactions. [ABSTRACT FROM AUTHOR]

A new ternary potassium cobalt stannide, K13CoSn17- x ( x = 0.1), was obtained by reacting the mixture of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. K13CoSn17- x ( x = 0.1) crystallizes in the orthorhombic space group Pbca (No. 61) with a = 26.2799(7) Å, b = 24.1541(6) Å, c = 29.8839(6) Å, V = 18969.3(8) Å3, and Z = 16. Its structure contains isolated [CoSn9] monocapped square antiprism and [Sn4] tetrahedron in the ratio 1:2, forming a hierarchical variant of Laves phase MgZn2. The structural relation between the title compound with MgZn2 as well as other binary stannides is also discussed. [ABSTRACT FROM AUTHOR]

Ba4AgGaS6 (I), Ba4AgGaSe6 (II), Ba4CuInS6 (III), and Ba4AgInS6 (IV) are prepared by solid-state reactions of the elements and/or binary chalcogenides (fused silica tube under Ar, 850-960 °C, 3-7 d). [ABSTRACT FROM AUTHOR]

Despite remarkable luminescent performance of 0D lead halide perovskites, achieving highly efficient blue light emission is extremely challenging and crucial for this domain. Considering the high toxicity of Pb2+ ion, it is significant to explore water‐stable lead‐free 0D halides as highly efficient and stable blue emitting materials. To address these issues, a family of 0D hybrid zinc halides of AZnBr4 (A = EP, BP, and TMPDA) based on discrete [ZnBr4]2− tetrahedrons is herein reported as desirable blue light emitters. The wide band gaps enable these 0D halides to display highly efficient blue light emissions (452–485 nm) with highest photoluminescence quantum yield (PLQY) of 35.47%. More importantly, all these 0D halides present extraordinary chemical stabilities in humid air and water for one month, and are also capable of withstanding extreme pH conditions in the range of 0–14, likely the widest observed pH range for perovskites. Notably, the ultrahigh chemical stabilities of 0D zinc halides are nearly unmatchable among all known literature perovskite materials to the best of the authors' knowledge. Combined superiorities of unusual blue light emission, promising PLQY, ultrahigh stability, and non‐toxicity highlight the potential optoelectronic applications in wide chemical environments for these 0D zinc halides. [ABSTRACT FROM AUTHOR]

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]2InxSb1−xCl7 ⋅ 6 H2O (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. [ABSTRACT FROM AUTHOR]

Two new zero-dimensional (0D) hybrid indium halides of [H2DMP]2InX7·2H2O (X = Cl, Br) were designed based on [InX6]3− octahedra as optically active centers. Remarkably, these 0D halides display intrinsic broadband yellow-orange light emissions with highest quantum yield of 58.53% exceeding all previously reported 0D indium halides. [ABSTRACT FROM AUTHOR]

Hybrid organic–inorganic lead halide perovskites (HOIPs) possess significant photoelectric characteristics for solar energy conversion, but the presence of lead causes issues for eco-friendly applications. Halide double perovskites represent a green option for application in the optoelectronic field, especially X-ray detection systems. Despite the great efforts, the exploration of large-size lead-free iodide-based hybrid double perovskite single crystals for X-ray detection has been unsuccessful. Herein, we demonstrate that a large single crystal of the 2D (two-dimensional) semiconducting perovskite (C6H16N2)2CuBiI8·0.5H2O can serve as an X-ray detection candidate. A perovskite crystal, as large as 35 × 31 × 3 mm3, was grown using a low-cost, simple cooling solution approach. To the best of our knowledge, this is the first time a centimeter-sized 2D BiCu iodide double perovskite single crystal has been used for X-ray detection. The perovskite crystal exhibited unique properties for X-ray detection, such as a significant X-ray absorption coefficient, considerable μτ product, and low trap density. Moreover, X-ray detection with a sensitivity of 5.51 μC Gyair−1 cm−2 was achieved based on a single crystal. This work opens new ways to explore specially designed organic cations for stabilizing 2D HOIPs that show great potential in optoelectronics. [ABSTRACT FROM AUTHOR]

X-ray detection plays an extremely significant function in medical diagnosis, nondestructive testing, safety testing, scientific research, environmental monitoring and other practical applications. However, conventional inorganic semiconductors, such as amorphous selenium, crystalline Si and pure Ge present almost uncontrollable bandgaps and require quite sophisticated fabrication techniques despite their outstanding performance. As developing materials for direct conversion X-ray detection, halide perovskite semiconductors exhibit remarkable properties with high sensitivity. In this review, we summarize the optoelectronic performance of different dimensional perovskites in X-ray detection and their application in X-ray imaging for perovskite-based X-ray detectors including single crystals, films and wafers. This review aims to preliminarily highlight the relationship between structural dimensionality and X-ray detection properties, which should provide valuable suggestions for researchers to rationally design high-performance halide perovskite X-ray photodetectors through crystal engineering at the molecular level in the future. [ABSTRACT FROM AUTHOR]

Organic-inorganic hybrid low-dimensional metal halides have been widely studied as a new class of luminescence materials due to abundant structural diversity and intriguing photophysical property. Herein, we explored two new Cd-based 0D halides of [BHEPZ]CdBr 4 (BHEPZ = 1,4-Bis(2-hydroxyethyl) piperazine) and [EPIPZ]CdBr 4 (EPIPZ = 1-ethylpiperazine) through facile wet-chemistry method. These 0D halides exhibit blue light emissions derived from radiative recombination of self-trapped excitons (STEs) based on detailed spectroscopy investigations. More interestingly, [BHEPZ]CdBr 4 exhibits rapid luminescence off switching toward benzaldehyde but fails in any other organic solvents. In-depth investigations demonstrate that the detection limit can fall to 2.65 ppm indicating perfect real-time fluorescent probe to detect benzaldehyde with high sensitivity and selectivity. This work enriches the cadmium halide materials and provide a new perspective for potential applications of 0D hybrid metal halides. Two Cd-based 0D halides were designed as blue light emitters from self-trapped excitons (STEs) with high thermal stability. Significantly, this halide displays fluorescence detection ability toward benzaldehyde with high selectivity, sensitivity and stability. [Display omitted] • Two 0D hybrid cadmium halides based on discrete [CdBr 4 ]2- clusters were synthesized. • The halides exhibits excellent chemical and thermal stabilities. • [BHEPZ]CdBr 4 can be explored as a good fluorescence sensor for benzaldehyde. [ABSTRACT FROM AUTHOR]

Low-dimensional hybrid antimony halide perovskites have fascinated the extensive research for their excellent photoluminescence behaviors. However, reasonable optimization of luminescence performance through molecule-level structural regulation remains a formidable challenge. The solution evaporation method with the reaction of organic amines and acid solutions of metal salts is a well-established method for the synthetic of low-dimensional hybrid antimony halide. In this work, by selecting organic cations with different sizes as template molecules, we have successfully synthesized three hybrid antimony halides of 0D [HDBA] 2 SbCl 5 (1), 0D [H 2 ATMP] 2 SbCl 7 (2) and 1D [H 3 PMDETA]Sb 2 Cl 9 (3) (DBA ​= ​dibutylamine, ATMP ​= ​4-amino-2,2,6,6-tetramethylpiperidine, PMDETA = N,N,N′,N″,N″-pentamethyldiethylenetriamine). by the solution evaporation method at room temperature for 2–5 days. These hybrid antimony halides exhibit broadband yellow-light with the highest photoluminescence quantum yield (PLQY) of 8.38%. According to detailed spectroscopy characterizations and theoretical calculations, the broadband light emissions should originate from self-trapped excitons (STEs). These antimony halides could be fabricated as white LEDs with highest color rendering index (>90%). The intrinsic broad-band light emissions and facile assembly process enable these hybrid antimony halides as promising candidates for yellow-light emitting materials. Structural design of hybrid antimony halide : Three antimony chlorides with different structures were prepared by facile solution method. These antimony chlorides have 0D pyramidal [SbCl 5 ]2- and 1D [Sb 2 Cl 9 ]3- chains, and display the broadband yellow-light emissions. [Display omitted] • Lead-free hybrid antimony halides with 0D pyramidal [SbCl 5 ]2- and 1D [Sb 2 Cl 9 ]3- chains. • Broadband yellow-light emissions originate from self-trapped excitons. • These hybrid antimony halides can be fabricated as white LEDs with high CRI. [ABSTRACT FROM AUTHOR]

One new manganese thiogermanate, [(dien)2Mn]Ge2S4 (dien=diethylenetriamine), was prepared under mild solvothermal conditions and structurally and spectroscopically characterized. The title compound crystallizes in the orthorhombic system, chiral space group P212121 (no. 19) with a=9.113(4) Å, b=12.475(5) Å, c=17.077(7) Å, V=1941.5(15) Å3 and Z=4. Its structure features a three-dimensional (3D) network composed of a one-dimensional (1D) [Ge2S4]2− anionic chain and a [(dien)2Mn]2+ complex interconnected via various hydrogen bonds. The most interesting structural feature of the compound is the presence of two different oxidation states of germanium centers in the 1D [Ge2S4]2− chain, which is also supported by the result of X-ray photoelectron spectroscopy measurement. The optical property of the title compound has also been studied by UV–vis spectra. [ABSTRACT FROM AUTHOR]

New 2D perovskites contain special 2D layers formed by the mix of corner- and edge- shared with [PbX 6 ] octahedrons, and display the broadband yellow-light emissions covering the whole visible region. [Display omitted] • New 2D perovskites composed of mixed corner- and edge-shared octahedron. • Broadband emission covering the whole entire visible light. • These 2D perovskites can be fabricated as white LEDs with high CRI. Herein, we reported two new 2D perovskites of [DAPMA] 2 Pb 3 X 12 ·2H 2 O (X = Cl (1), Br (2), DAPMA = N,N-Bis(3-aminopropyl)methylamine) containing special 2D [Pb 3 X 12 ]6− layers formed by mixed corner- and edge-shared [PbX 6 ] octahedrons. Both compounds 1 and 2 exhibit broadband yellow light emissions with promising photoluminescence quantum yields of 4.84% and 3.02%, respectively. According to detailed spectroscopy characterizations, the broadband light emissions should originate from self-trapped excitons (STEs). In addition, these 2D perovskites can be fabricated as white LEDs with highest color rendering index of 96.3%. This work provides a new type of structural model to probe into the relationship between luminescence behavior and structure. [ABSTRACT FROM AUTHOR]

One new bulk lead-free 0D antimony halide of [DPA] 3 SbCl 6 was designed as greenish-yellow light emitter with near-unity PLQY. Thorugh elaborate fabrication toward [DPA] 3 SbCl 6 , multiple reversible photoluminescence on/off switch was achieved with important potential in anti-counterfeiting and confidential information encryption-decryption technologies, which opens a new way to design perovskite materials for new optoelectronic applications. [Display omitted] • New 0D antimony halide as efficient green emitter with remarkable near-unity PLQY. • Applied as luminescent ink against high-resolution anti-counterfeiting application. • Fast information encryption decryption achieved through solid/liquid dual mode. • Multiple reversible PL on/off switches enhancement information encryption decryption. Storage and protection of confidential information is an increasing challenge for global digital economy, which stimulates the never-ending pursuit of high-security technology to prevent information forgery and leakage. Herein, we develop a novel approach to realize controllable information encryption-decryption based on reversible photoluminescence (PL) on/off switch in 0D hybrid antimony halide. A new 0D [DPA] 3 SbCl 6 (DPA = dipropylamine) was designed as broadband green light emitter with near-unity photoluminescence quantum yield. Benefiting from invisible and non-luminescent superiorities of SbCl 3 , information encrypted by SbCl 3 pattern can′t be directly decoded upon common light excitations. Under the trigger of [DPA]Cl salt, superfast transition from SbCl 3 to [DPA] 3 SbCl 6 gives rise to highly efficient emission and thus effective information decoding. Subsequently, through methanol impregnation and desolvation strategy, luminescence of [DPA] 3 SbCl 6 can be easily quenched and recovered resulting in reversible PL on/off switching. The multiple and controllable PL emission conversion provides a dual-mode confidential information encryption-decryption technology. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three new one-dimensional (1D) face-shared octahedral perovskites were synthesized by using different types of organic cations. • These 1D perovskites exhibit tunable broadband luminescence from orange to blue light emissions. • Systematical characterizations unveil that these broadband emissions are derived from the radiative recombination of self-trapped excitons due to strong electron–phonon coupling. Three new one-dimensional (1D) face-shared octahedral perovskites with unified APbBr 3 composition, namely, [DTHPE]Pb 2 Br 6 (1), [TMPDA]PbBr 3 (2) and [MPD]PbBr 3 (3) have been synthesized by using different types of organic cations. These 1D perovskites exhibit tunable broadband luminescence from orange to blue light emissions. Experimental and computational studies unveil that these broadband emissions are derived from the radiative recombination of self-trapped excitons due to strong electron–phonon coupling. [ABSTRACT FROM AUTHOR]

Luminescent materials with engineered optical properties play an important role in anti-counterfeiting and information security technology. However, conventional luminescent coding is limited by fluorescence color or intensity, and high-level multi-dimensional luminescent encryption technology remains a critically challenging goal in different scenarios. To improve the encoding capacity, we present an optical multiplexing concept by synchronously manipulating the emission color and decay lifetimes of room-temperature phosphorescence materials at molecular level. Herein, we devise a family of zero-dimensional (0D) hybrid metal halides by combining organic phosphonium cations and metal halide tetrahedral anions as independent luminescent centers, which display blue phosphorescence and green persistent afterglow with the highest quantum yields of 39.9 % and 57.3 %, respectively. Significantly, the luminescence lifetime can be fine-tuned in the range of 0.0968-0.5046 μs and 33.46-125.61 ms as temporary time coding through precisely controlling the heavy atomic effect and inter-molecular interactions. As a consequence, synchronous blue phosphorescence and green afterglow are integrated into one 0D halide platform with adjustable emission lifetime acting as color- and time-resolved dual RTP materials, which realize the multiple applications in high-level anti-counterfeiting and information storage. The color-lifetime-dual-resolved encoding ability greatly broadens the scope of luminescent halide materials for optical multiplexing applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

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) 2 ZnX 4 (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 [ZnX 4 ] 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.)

Low-dimensional organic-inorganic hybrid lead halide perovskites have attracted much interest in solid-state lighting and displays, but the toxicity and instability of lead halide are obstacles to their industrial applications, which must be overcome. As an alternative, Cu(I)-based hybrid metal halides have emerged as a new type of luminescent material owing to their diversified structure, adjustable luminescence, low toxicity and low cost. Herein, we report three one-dimensional (1D) hybrid Cu(I)-based halides with the general formula ACu 2 Br 4 (A = [(Me) 4 -Pipz] 2+ and [BuDA] 2+ and [TMEDA] 2+ ). These 1D hybrid Cu(I) halides display stable broadband blue emission with maximum emission peaks in the range of 445-474 nm and the highest photoluminescence quantum yield of 37.8%. Furthermore, in-depth experimental and theoretical investigations revealed that the broadband blue emissions originate from the radiative recombination of self-trapped excitons. Most importantly, there is no structural degradation and attenuation of emission intensity even after continuously soaking these halides in water for at least two months, demonstrating their ultra-high anti-water stability. Hirshfeld surface analysis shows that a large number of weak hydrogen bonds can protect the inorganic skeleton from degradation due to water. This work provides a new strategy for the design of water-stable Cu(I)-based halides with efficient blue emission and wide potential applications in humid environments.

Although metal halide-based X-ray scintillators have obtained significant development with adjustable radioluminescent spectral range, the red light-emitting scintillator has been sparsely reported and remains a great challenge until now. To remedy this research blank, we investigated the scintillating property of red light-emissive one-dimensional (1D) organic manganese halide of (MBIZ)(MnCl 3 H 2 O)·H 2 O (MBIZ = 2-methyl-1H-benzoimidazolium) with a high PLQY of 71% under UV light excitation. Remarkably, this manganese halide single crystal exhibits a compelling X-ray scintillating property in the red light spectral range with a light yield of 19 600 photons MeV -1 and detection limit of 0.204 μGy/s, which is significantly better than the standard dosage for X-ray diagnostics. Furthermore, this manganese halide also exhibits excellent radiation resistance ability toward long-term continuous irradiation of high-dose X-ray with stable radiophotoluminescence intensity. Benefiting from the abovementioned combined merits, (MBIZ)(MnCl 3 H 2 O)·H 2 O demonstrates high-performance X-ray imaging with an outstanding spatial resolution of 11.1 lpmm -1 . As far as we know, this is an infrequent red-emissive X-ray scintillator in metal halide materials, which highlights a successful structural design concept to explore new manganese halides as more desirable scintillators and expand the application field in medical diagnosis.

A new one-dimensional hybrid [APCHA]Cu 2 I 4 was designed and applied as an X-ray scintillator. It exhibits broad-band green emission with a high PLQY of 74.80% and excellent stability. It demonstrates radioluminescence property with a light yield of 28 336 photons MeV -1 , detection limit of 41 nGy air s -1 , and high spatial limit of 13.95 lp mm -1 in X-ray imaging.

Although organic-inorganic hybrid Mn 2+ halides have advanced significantly, achieving high stability and narrow-band emission remains enormously challenging owing to the weak ionic nature and soft crystal lattice of the halide structure. To address these issues, we proposed a cationic engineering strategy of long-range cation π···π stacking and C-H···π interactions to simultaneously improve the crystal structural stability and rigidity. Herein, two organic zero-dimensional (0D) manganese halide hybrids of (BACQ) 2 MnX 4 [BACQ = 4-(butylamino)-7-chloroquinolin-1-ium; X = Cl and Br] were synthesized. (BACQ) 2 MnX 4 display strong green-light emissions with the narrowest full width at half-maximum (fwhm) of 39 nm, which is significantly smaller than those of commercial green phosphor β-SiAlON:Eu 2+ and most of reported manganese halides. Detailed Hirshfeld surface analyses demonstrate the rigid environment around the [MnX 4 ] 2- units originating from the interactions between [BACQ] + . The rigid crystal structure weakens the electron-phonon coupling and renders narrow fwhm of these manganese halides, which is further confirmed by temperature-dependent emission spectra. Remarkably, (BACQ) 2 MnX 4 realizes outstanding structural and luminescence stabilities in various extreme environments. Benefiting from the excellent performance, these Mn 2+ halides are used to assemble light-emitting diodes with a wide color gamut of 105% of the National Television System Committee 1931 standard, showcasing the advanced applications in liquid-crystal-display backlighting.

A quantitative water detection method is urgently needed in storage facilities, space exploration, and the chemical industry. Although numerous physical techniques have been widely utilized to determine the water content, they still suffer from many disadvantages such as highly expensive special instruments, complicated analysis processes, etc. Hence, a convenient, rapid, and sensitive water analysis method is highly desirable. Herein, we developed a visual fluorescence sensing technology for water detection based on reversible PL off-on switching of organic-inorganic hybrid zero-dimensional (0D) manganese halides. In this work, a family of hybrid manganese halides were synthesized through a facile solution method, namely, [NH 4 (18-Crown-6)] 2 MnBr 4 , [Ca(18-Crown-6)·3H 2 O](18-Crown-6)MnBr 4 , [NH 4 (dibenzo-18-Crown-6)] 2 MnBr 4 , and [Ca(dibenzo-18-Crown-6)·2H 2 O]MnBr 4 . Excited by UV light, these highly crystalline manganese halides exhibit strong green light emissions from the d-d electron transition of Mn 2+ with near-unity photoluminescence quantum yield and submillisecond lifetime. Benefiting from the dynamic and weak ionic bonding interactions, these 0D manganese halides display reversible water-response on/off luminescence switching but fail in any other aprotic solvents. Therefore, these 0D hybrid manganese halides can be explored as ultrafast visual fluorescence probes to detect the trace amount of water in organic solvents with multiple superiorities of rapid response time (< 2 s), ultralow detection limit (9.71 ppm), excellent repeatability, etc. The reversible water-response luminescent on/off switching also provides a binary optical gate with advanced applications in anticounterfeiting and information security, etc.

Considering the instability and toxicity of 3D Pb-based perovskite nanocrystals, lead-free low-dimensional organic-inorganic hybrid metal halides have attracted widespread attention as potential substitutes. Herein, two new tin-based 0D halides [H 4 BAPP]SnBr 5 ·Br and [H 4 BAPP]SnCl 5 ·Cl·H 2 O (BAPP = 1,4-bis(3-aminopropyl)piperazine) were synthesized successfully based on [SnX 5 ] 3- as an emission center. Typically, [H 4 BAPP]SnBr 5 ·Br and [H 4 BAPP]SnCl 5 ·Cl·H 2 O display broadband yellow and yellow-green light emissions originating from the radiative recombination of self-trapped excitons (STEs). The photoluminescence quantum yields (PLQYs) of the two compounds were calculated to be 19.27% and 2.36%, respectively. Furthermore, the excellent chemical and thermal stability and broadband light emissions reveal their potential application in solid-state white lighting diodes.

Environmentally friendly and highly efficient blue luminescent materials are an unremitting pursuit in the optoelectronic field. Herein, we assembled a new 0D lead-free metal halide of (F-PPA)ZnBr4, which exhibits narrow blue light emission with a remarkable PLQY of 50.15%, high stability and high detection sensitivity toward UV light. These results indicate the potential for the application of low-dimensional zinc-based halides in multiple optoelectronic devices.

The increasing demands in optoelectronic applications have driven the advancement of organic-inorganic hybrid metal halides (OIMHs), owing to their exceptional optical and scintillation properties. Among them, zero-dimensional (0D) low-toxic manganese-based scintillators have garnered significant interest due to their exceptional optical transparency and elevated photoluminescence quantum yields (PLQYs), making them promising for colorful light-emitting diodes and X-ray imaging applications. In this study, two OIMH single crystals of (Br-PrTPP) 2 MnBr 4 (Br-PrTPP = (3-bromopropyl) triphenylphosphonium) and (Br-BuTPP) 2 MnBr 4 (Br-BuTPP = (4-bromobutyl) triphenylphosphonium) were prepared via a facile saturated crystallization method. Benefiting from the tetrahedrally coordinated [MnBr 4 ] 2- polyhedron, both of them exhibited strong green emissions peaked at 517 nm owing to the d-d electron transition of Mn 2+ with near-unity PLQYs of 99.33 and 86.85%, respectively. Moreover, benefiting from the high optical transparencies and remarkable luminescence properties, these manganese halides also exhibit excellent radioluminescent performance with the highest light yield of up to 68,000 photons MeV -1 , negligible afterglow (0.4 ms), and linear response to X-ray dose rate with the lowest detection limit of 45 nGy air s -1 . In X-ray imaging, the flexible film made by the composite of (Br-PrTPP) 2 MnBr 4 and PDMS shows an ultrahigh spatial resolution of 12.78 lp mm -1 , which provides a potential visualization tool for X-ray radiography.

Zero-dimensional (0D) hybrid metal halides have emerged as highly efficient luminescent materials, but integrated multifunction in a structural platform remains a significant challenge. Herein, a new hybrid 0D indium halide of (Im-BDMPA)InCl 6 ·H 2 O was designed as a highly efficient luminescent emitter and X-ray scintillator toward multiple optoelectronic applications. Specifically, it displays strong broadband yellow light emission with near-unity photoluminescence quantum yield (PLQY) through Sb 3+ doping, acting as a down-conversion phosphor to fabricate high-performance white light emitting diodes (WLEDs). Benefiting from the high PLQY and negligible self-absorption characteristics, this halide exhibits extraordinary X-ray scintillation performance with a high light yield of 55 320 photons per MeV, which represents a new scintillator in 0D hybrid indium halides. Further combined merits of a low detection limit (0.0853 μGy air s -1 ), ultra-high spatial resolution of 17.25 lp per mm and negligible afterglow time (0.48 ms) demonstrate its excellent application prospects in X-ray imaging. In addition, this 0D halide also exhibits reversible luminescence off-on switching toward tribromomethane (TBM) but fails in any other organic solvents with an ultra-low detection limit of 0.1 ppm, acting as a perfect real-time fluorescent probe to detect TBM with ultrahigh sensitivity, selectivity and repeatability. Therefore, this work highlights the multiple optoelectronic applications of 0D hybrid lead-free halides in white LEDs, X-ray scintillation, fluorescence sensors, etc., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Halide perovskite nanocrystal (PNC) of 3D CsPbX 3 as a scintillator has aroused intensive attention with advanced applications in radiation detection and X-ray imaging. However, the low light yield and serious toxicity of Pb 2+ severely hinder advanced optoelectronic applications. To reduce these fatal shortcomings, a family of new environmentally friendly 0D hybrid lead-free indium halides of [DADPA]InX 6 ·H 2 O (DADPA = 3,3'-diaminodipropylamine; X = Cl and Br) was prepared. Upon UV excitation, these halides display strong broadband yellow-orange light emissions, and the photoluminescence quantum yield (PLQY) can be optimized up to near unity through the Sb 3+ -doping strategy. Significantly, high PLQY, negligible self-absorption and low attenuation ability toward X-ray render extraordinary scintillation performance with a high light yield of 51 875 photons MeV -1 and ultralow detection limit of 98.3 nGy air s -1 , which is far superior to typical 3D PNC scintillators. Additionally, the ultra-high spatial resolution of 25.15 lp mm -1 , negligible afterglow time (2.75 ms) and robust radiant stability demonstrates excellent X-ray imaging performance. To the best of our knowledge, this is the first report on X-ray scintillation based on 0D indium halide materials.

Exploring highly efficient blue-emissive lead-free halide materials is a significant and challenging objective in the study of luminescent materials. This study reports the synthesis of a new zero-dimensional (0D) hybrid zinc halide of [CYP]ZnBr 4 (CYP = 1-cyclohexylpiperazine) containing an isolated [ZnBr 4 ] 2- tetrahedron. [CYP]ZnBr 4 exhibits strong blue light emission with a high photoluminescence quantum yield (PLQY) of 79.22%, surpassing all previously reported 0D zinc halide counterparts. According to the theoretical and experimental studies, the blue light emission is attributed to intrinsic self-trapped excitons resulting from strong electron-phonon coupling and structural deformation. Importantly, [CYP]ZnBr 4 demonstrates excellent structural and luminescence stability toward high temperatures (180 °C) over at least half a month. High luminescence efficiency and stability enable [CYP]ZnBr 4 to be an efficient blue phosphor to fabricate white light-emitting diodes (LEDs), which produces high-quality white light with a color rendering index (CRI) of 93.1 and a correlated color temperature (CCT) of 5304 K, closely resembling natural sunlight. This white LED also exhibits consistent performance and stability across different drive currents, suggesting the potential for high-power optoelectronic applications. Overall, this study paves the way for the utilization of 0D hybrid halides in advanced solid-state lighting applications.

Herein, we for the first time report a reversible conversion between green-emissive [DMPZ]MnCl 4 and red-emissive [DMPZ] 4 (MnCl 6 )(MnCl 4 ) 2· (H 2 O) 2 (DMPZ = 1,4-dimethylpiperazine) using kinetic and thermodynamic controlling strategies. Significantly, the synchronous structural and emission transformations in single-component organic manganese halides with adjustable emission colors are highlighted.

In the relentless pursuit of developing high-performance, stable and environmentally friendly materials for X-ray detection, we present a new class of Bi-based hybrid organic-inorganic perovskites. An X-ray detector based on a new zero-dimensional (0D) triiodide-induced lead-free hybrid perovskite, (DPA)2BiI9 (DPA = C 5 H 16 N 2 2+ ), has been developed demonstrating outstanding detection performance, including high X-ray sensitivity (20 570 μC Gy air -1 cm -2 ), low detectable dose rate (0.98 nGy air s -1 ), fast response time (154/162 ns) and excellent long-term stability.

Organic-inorganic hybrid low-dimensional lead halides have garnered significant interest in the realm of solid-state optical materials due to their unique properties and potential applications. In this study, we report the synthesis, characterization and application of Mn 2+ -doped one-dimensional (1D) [AEP]PbCl 5 ·H 2 O hybrid lead halide perovskites with tunable photoluminescence properties. The Mn 2+ doping leads to a redshift of the dominant emission wavelength from 463 nm to 630 nm, with the optimal doping concentration resulting in an enhanced photoluminescence quantum yield (PLQY) from less than 1% to 8.96%. The structural and optical stability of these doped perovskites have been thoroughly investigated revealing excellent performance under humid and high-temperature conditions. Perovskite-PVP composite films exhibit high crystallization and bright orange-red emission under UV excitation. Furthermore, we demonstrate the successful fabrication of a white LED device using the Mn 2+ -doped perovskite in combination with commercial green and blue phosphors. The fabricated LED exhibits a high color rendering index (CRI) of 87.2 and stable electroluminescence performance under various operating currents and extended operation times. Our findings highlight the potential of Mn 2+ -doped 1D hybrid lead halide perovskites as efficient and stable phosphors for high-performance white light emitting diodes and other optoelectronic applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Lead halide perovskites have been explored as a new kind of promising X-ray with wide applications in radiation-associated fields, but low light yield and serious toxicity extremely restrict further applications. To address these issues, we herein demonstrated one new zero-dimensional (0D) organic-inorganic hybrid cuprous halide of [BAPMA]Cu 2 Br 5 (BAPMA = N , N -Bis(3-aminopropyl) methylamine) containing discrete [Cu 4 Br 10 ] 6- tetramers as excellent lead-free scintillators. Upon UV light excitation, [BAPMA]Cu 2 Br 5 displays highly efficient broadband yellowish-green light emission with one dominant peak at 526 nm, a large Stokes shift of 244 nm, and a high photoluminescent quantum yield of 53.40%. Significantly, this broadband light emission can also be excited by higher-energy X-ray as radioluminescence with a high scintillation light yield of 43,744 photons/MeV. The detection limit of 0.074 μGy air /s is also far less than the required value for regular medical diagnostics of 5.5 μGy air/ s. The solution-assembled hybrid structure facilely enables the [BAPMA]Cu 2 Br 5 -based scintillation screen to display high-performance X-ray imaging with a spatial resolution of 15.79 lp/mm showcasing potential application in X-ray radiography. In brief, combined merits of low toxicity and cost, negligible self-absorption, a low detection limit, considerable light yield, and spatial resolution highlight the excellent scintillation performance of 0D hybrid cuprous halide.

Intelligent stimuli-responsive fluorescence materials are extremely pivotal for fabricating luminescent turn-on switching in solid-state photonic integration technology, but it remains a challenging objective for typical 3-dimensional (3D) perovskite nanocrystals. Herein, by fine-tuning the accumulation modes of metal halide components to dynamically control the carrier characteristics, a novel triple-mode photoluminescence (PL) switching was realized in 0D metal halide through stepwise single-crystal to single-crystal (SC-SC) transformation. Specifically, a family of 0D hybrid antimony halides was designed to exhibit three distinct types of PL performance including nonluminescent [Ph 3 EtP] 2 Sb 2 Cl 8 ( 1 ), yellow-emissive [Ph 3 EtP] 2 SbCl 5 ·EtOH ( 2 ), and red-emissive [Ph 3 EtP] 2 SbCl 5 ( 3 ). Upon stimulus of ethanol, 1 was successfully converted to 2 through SC-SC transformation with enhanced PL quantum yield from ~0% to 91.50% acting as "turn-on" luminescent switching. Meanwhile, reversible SC-SC and luminescence transformation between 2 and 3 can be also achieved in the ethanol impregnation-heating process as luminescence vapochromism switching. As a consequence, a new triple-model turn-on and color-adjustable luminescent switching of off-on I -on II was realized in 0D hybrid halides. Simultaneously, wide advanced applications were also achieved in anti-counterfeiting, information security, and optical logic gates. This novel photon engineering strategy is expected to deepen the understanding of dynamic PL switching mechanism and guide development of new smart luminescence materials in cutting-edge optical switchable device.

Rewritable luminescent paper is particularly crucial, considering the ultrahigh paper consumption and confidential information security, but a highly desirable stimuli-responsive smart luminescent material with excellent water solubility has rarely been studied. Herein, a new type of rewritable paper made by highly efficient green light emissive zero-dimensional (0D) organic manganese halides is rationally designed by virtue of the reversible photoluminescence (PL) off-on switching. Specifically, the green emission can be linearly quenched by water vapor in a wide humidity range and again recovered in a dry atmosphere, which make it a smart hydrochromic PL off-on switching and humidity sensor. Benefiting from the reversible luminescence off-on switch and excellent water solubility, rewritable luminescent paper is realized through water-jet security printing technology on 0D halide-coated commercial paper with high resolution. The printed/written information can be easily cleaned by slight heating with outstanding "write-erase-write" cycle capabilities. In addition, multiple light source-induced coincident green light emissions further provide convenience to realize anti-counterfeiting, encryption and decryption of confidential information, and so forth. This work highlights the superiority of dynamic ionic-bonded 0D organic manganese halides as reversible PL switching materials in rewritable luminescent paper, high-security-level information printing, storage and protection technologies, and so forth.