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Abstract: Three new ternary potassium(I) zinc(II) or cadmium(II) tellurides, namely, K2Cd2Te3, K6CdTe4 and K2ZnTe2, were synthesized by solid-state reactions of the mixture of pure elements of K, Cd (or Zn) and Te in Nb tubes at high temperature. K2Cd2Te3 belongs to a new structure type and its structure contains a novel two-dimensional [Cd2Te3]2− layers perpendicular to the b-axis. K(5) cation is located at the center of five member rings of the 2D [Cd2Te3]2− layer, whereas other K+ cations occupy the interlayer space. K6CdTe4 with a K6HgS4 type structure features a “zero-dimensional” structure composed of isolated CdTe4 tetrahedra separated by the K+ ions. K2ZnTe2 in the K2ZnO2 structural type displays 1D [ZnTe2]2− anionic chains of edge sharing [ZnTe4] tetrahedra separated by the potassium(I) ions. K2Cd2Te3, K6CdTe4 and K2ZnTe2 revealed a band gap of 1.93, 2.51 and 3.0eV, respectively. [Copyright &y& Elsevier]

Rationally optimizing the photoluminescence performance via accurate structural modulation is one of most important and challenging issues for hybrid halides. Herein, a viable crystal dimensional reduction strategy is proposed to reasonably enhance the photoluminescence quantum yield (PLQY) of hybrid antimony halide. Specifically, a synthetic technique is developed and new 1D [DMPZ]SbCl5 ∙ H2O (DP‐SbCl5) is sliced to 0D [DMPZ]2SbCl6 ∙ Cl ∙ (H2O)2 (DP‐SbCl6) with crystal dimensional reduction from infinite [SbCl5]2− chain to discrete [SbCl6]3− octahedron. Comparing with nonluminescent 1D DP‐SbCl5, 0D DP‐SbCl6 displays highly efficient broadband yellow light emission with enhanced PLQY up to 75.94%. First‐principles calculation demonstrates that 0D DP‐SbCl6 features more flat and narrow band structure, which promotes the photoelectron localization and increases the quantum confinement, and finally boosts the luminescence efficiency. Together highly efficient and ultra‐stable luminescence performance enable DP‐SbCl6 as excellent down‐conversion broadband yellow phosphor to successfully fabricate white light emitting diodes with a high color rendering index of 92. This work provides a novel structural modulation strategy of crystal dimensional reduction to rationally optimize the PL performance of hybrid metal halides. [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]

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 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]

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]

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.

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)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.)

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.

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.

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.

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.

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.)

Two new zero-dimensional (0D) hybrid indium halides of [H 2 DMP] 2 InX 7 ·2H 2 O (X = Cl, Br) were designed based on [InX 6 ] 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.

Two-dimensional hybrid lead perovskites have attracted a great deal of attention in white-light-emitting diodes, but the serious toxicity of Pb 2+ and the limited photoluminescence quantum yield (PLQY) still restrict further optoelectronic application. To address these issues, a new combining photon strategy was proposed to achieve highly efficient broadband white-light emission in a new family of zero-dimensional (0D) indium halides based on an [InCl 6 ] 3- octahedron. Remarkably, these 0D halides display dual-band white-light emission derived from the synergistic work of blue- and yellow-light-emitting bands, which can be ascribed to the radiative recombination of bound excitons in organic cations and self-trapped excitons in inorganic anions, respectively, based on spectroscopy and theoretical studies. In-depth first-principles calculation demonstrates that the increased structural deformability effectively improves the PLQY from 7.01% to 18.56%. As a proof of concept, this work provides a profound understanding for advancing the rational design of novel single-component 0D lead-free halides as high-performance white-light emitters.

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 (C 6 H 16 N 2 ) 2 CuBiI 8 ·0.5H 2 O can serve as an X-ray detection candidate. A perovskite crystal, as large as 35 × 31 × 3 mm 3 , 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 Gy air -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.

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.)

Low-dimensional organic-inorganic hybrid metal halide materials have been extensively studied due to their excellent optoelectronic performances. Herein, by using the facile wet-chemistry method, we designed one new hybrid cadmium bromide of (H 3 AEP) 2 CdBr 6 ·2Br based on discrete octahedral [CdBr 6 ] 4- units. Remarkably, the bulk crystal of (H 3 AEP) 2 CdBr 6 ·2Br exhibits strong broadband orange-red light emission from the radiative recombination of self-trapped excitons (STEs) with a high photoluminescence quantum yield (PLQY) of 9%. Benefiting from the highly efficient luminescent performance, this 0D cadmium perovskite can be utilized as an excellent down-conversion red phosphor to assemble a white light-emitting diode, and a high color rendering index (CRI) of 93 is realized. As far as we know, this is the first orange-red light-emitting hybrid cadmium perovskite which promotes the full-color display in this system.

Herein, a new organic-inorganic hybrid cuprous iodide of [(Me) 2 -DABCO]Cu 6 I 8 was prepared and structurally characterized with a novel three-dimensional (3D) [Cu 6 I 8 ] 2- framework. Significantly, this 3D cuprous iodide displays infrequent broadband red-to-near-infrared light emission (600-1000 nm) stemming from the radiative recombination of self-trapped excitons.

In recent years, low-dimensional lead halides have emerged as some of most attractive photoelectric materials due to their intrinsic broadband emissions with a potential application in white-light emitting diodes. To achieve the desired performance, tremendous research has emphasized the modulation of inorganic components as optical centers; however, less work has paid attention to the direct contribution of the organic components. Herein, we successfully assembled two new hybrid lead halides of [H 2 BPP]Pb 2 X 6 (X = Br, 1 , and Cl, 2 ) containing one-dimensional double [Pb 2 X 6 ] 2- chains using optically active 1,3-bis(4-pyridyl)-propane (BPP) as an organic cation. Under UV-light excitation, compounds 1 and 2 exhibit broadband yellowish-green emissions, which were verified by promising photoluminescence quantum efficiencies (PLQEs) of 8.10% and 4.84%, respectively. The broadband light emissions are derived from the combination of dual higher-energy blue and lower-energy yellow light spectra, which can be attributed to the individual contributions of the organic and inorganic components, respectively, according to the time-resolved and temperature-dependent emission spectra as well as theoretical calculations. This work proves the great contribution of organic components to the photophysical properties and provides a new design strategy to realize broadband light emission by rationally combining the dual-emitting properties of different assembly blocks.

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.)

The development of new visible light-driven photocatalysts based on semiconducting materials remains a greatly interesting and challenging task for the purpose of solving the energy crisis and environmental issues. By using photosensitive [(Me) 2 -2,2'-bipy] 2+ (1,1'-dimethyl-2,2'-bipyridinium) cation as template, we synthesized one new type of inorganic-organic hybrid cuprous and silver halogenides of [(Me) 2 -2,2'-bipy]M 8 X 10 (M = Cu, Ag, X = Br, I). The compounds feature a three-dimensional anionic [M 8 X 10 ] 2- network composed of a one-dimensional [M 8 X 12 ] chain based on MX 4 tetrahedral units. The photosensitization of organic cationic templates results in narrow band gaps of hybrid compounds (1.66-2.06 eV), which feature stable visible light-driven photodegradation activities for organic pollutants. A detailed study of the photocatalytic mechanism, including the photoelectric response, photoluminescence spectra, and theoretical calculations, shows that the organic cationic template effectively inhibits the recombination of photoinduced electron-hole pairs leading to excellent photocatalytic activities and photochemical stabilities.

By using transition-metal (TM) complex cationic dyes as structure-directing agents and photosensitizers, a series of inorganic-organic hybrid metal halides, namely, [TM(2,2'-bipy) 3 ]AgPb 2 I 7 [TM = Ni (1), Co (2) and Zn (3)], [Co(2,2'-bipy) 3 ]CuPb 2 Br 7 (4) and [TM(2,2'-bipy) 3 ]AgPb 2 Br 7 [TM = Ni (5) and Fe (6)], have been solvothermally prepared and structurally characterized. Compounds 1-3 feature 1D [AgPb 2 I 7 ] 2- chains built from the condensation of [Ag 2 I 6 ] dimers and [Pb 4 I 14 ] tetramers, and compounds 4, 5 and 6 contain similar 1D [CuPb 2 Br 7 ] 2- and [AgPb 2 Br 7 ] 2- chains, respectively. UV-Vis diffuse reflectance measurements reveal narrow band gaps of 1.75-2.18 eV for compounds 1-6, which lead to efficient and stable photocatalytic degradation activities over organic pollutants under visible light irradiation. Among the title compounds, sample 5 shows the highest photocatalytic degradation activity. The possible mechanism for their stable photocatalytic activities is proposed based on the experimental and theoretical studies.

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.)

The new two-dimensional coordination polymer, poly[(μ4-1-phenyl-1H-1,2,3,4-tetrazole-5-thiolato)copper(I)], [Cu(C7H5N4S)]n, has been prepared under solvothermal conditions by reacting CuBr with 1-phenyl-1H-1,2,3,4-tetrazole-5-thiol (Hptt) in an acetonitrile and acetone solution. In the crystal structure, each Cu(I) ion is coordinated by two N atoms and two S atoms from four ptt(-) ligands, and each ptt(-) ligand links four Cu(I) 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.