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Although organic–inorganic hybrid Mn2+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)2MnX4[BACQ = 4-(butylamino)-7-chloroquinolin-1-ium; X = Cl and Br] were synthesized. (BACQ)2MnX4display 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:Eu2+and most of reported manganese halides. Detailed Hirshfeld surface analyses demonstrate the rigid environment around the [MnX4]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)2MnX4realizes outstanding structural and luminescence stabilities in various extreme environments. Benefiting from the excellent performance, these Mn2+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.

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)2MnBr4(Br-PrTPP = (3-bromopropyl) triphenylphosphonium) and (Br-BuTPP)2MnBr4(Br-BuTPP = (4-bromobutyl) triphenylphosphonium) were prepared via a facile saturated crystallization method. Benefiting from the tetrahedrally coordinated [MnBr4]2–polyhedron, both of them exhibited strong green emissions peaked at 517 nm owing to the d–d electron transition of Mn2+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 nGyairs–1. In X-ray imaging, the flexible film made by the composite of (Br-PrTPP)2MnBr4and PDMS shows an ultrahigh spatial resolution of 12.78 lp mm–1, which provides a potential visualization tool for X-ray radiography.

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]ZnBr4(CYP = 1-cyclohexylpiperazine) containing an isolated [ZnBr4]2–tetrahedron. [CYP]ZnBr4exhibits 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]ZnBr4demonstrates excellent structural and luminescence stability toward high temperatures (180 °C) over at least half a month. High luminescence efficiency and stability enable [CYP]ZnBr4to 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.

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]Cu2Br5(BAPMA = N,N-Bis(3-aminopropyl) methylamine) containing discrete [Cu4Br10]6–tetramers as excellent lead-free scintillators. Upon UV light excitation, [BAPMA]Cu2Br5displays 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 μGyair/s is also far less than the required value for regular medical diagnostics of 5.5 μGyair/s. The solution-assembled hybrid structure facilely enables the [BAPMA]Cu2Br5-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.

Halide perovskite nanocrystal (PNC) of 3D CsPbX3as 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 Pb2+severely hinder advanced optoelectronic applications. To reduce these fatal shortcomings, a family of new environmentally friendly 0D hybrid lead-free indium halides of [DADPA]InX6·H2O (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 Sb3+-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−1and ultralow detection limit of 98.3 nGyairs−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.

X-ray scintillators as functional energy materials possess the powerful ability to convert high-energy radiation into visible light with wide applications in various nuclear radiation fields. In this regard, three-dimensional (3D) lead perovskite nanocrystal-based X-ray scintillators have attracted extensive attention, but their low light yield and serious toxicity extremely restrict their further applications. To address these issues, a family of 0D hybrid cuprous halides of A2Cu4X6(A = PTPP, TPA; X = Br, I) based on discrete [Cu4X6]2−nanoclusters were demonstrated as highly desirable lead-free scintillators. Upon excitation of both ultraviolet and blue light, these halide nanoclusters displayed that self-trapped excitons induced broadband light emissions from green to red with near-unity photoluminescent quantum yield (PLQY, 93.1%) andlarge Stokes shifts (>1.3 eV). Significantly, the high PLQY, negligible self-absorption, and strong X-ray attenuation from [Cu4X6]2−nanoclusters endowed them with extraordinary radioluminescence properties. The linear radioluminescence intensity response to a wide range of X-ray dose rates gave an acceptable detection limit of 0.7563 µGyairs−1, which was lower than the required value for regular medical diagnostics (5.5 µGyairs−1). X-ray imaging demonstrated an ultrahigh spatial resolution of 14.83 lp mm−1and negligible afterglow (1.3 ms), showcasing potential applications in X-ray radiography. Overall, the combined superiorities of nontoxicity, high light yield, excellent stability, and good radiation hardness make cuprous halide nanoclusters excellent scintillators.

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.

Traditional white light-emitting diode (WLED) is mainly depending on coating broadband yellow phosphors (520–700 nm) on blue emitting LED chip (440–460). However, too strong blue light and absence of cyan light results in incongruous emission strength and low color rendering index (CRI), which cause serious damage to retina of eye. To overcome these shortcomings, cyan light emitting phosphor is highly desirable for the full-visible-spectrum LED with high CRI, but bright cyan phosphor remains rare. Herein, a new 0D hybrid copper(I) halide of [TMPDA]Cu2I6(TMPDA = N,N,2,2-tetramethyl-1,3-propylenediamine) single crystal is reported as a cyan light emitter with mominant emission wavelength at 489 nm, photoluminescence quantum yield of 26.66 % and large Stokes shift of 198 nm exceeding most of organic-inorganic metal halides. Remarkably, the single crystals display stable emission in various polar organic solvents and high temperature with sufficient emitting stability. More significantly, this 0D cuprous halide act as down-conversion cyan phosphor to fabricate WLED with a high CRI of 95 by reducing the cyan gap. In this study, we demonstrate an optical engineering strategy to prepare efficient cyan light emitting 0D cuprous halide and assembly high-performance WLED.

Considering low photoluminescence quantum yield (PLQY < 5%) of blue emissive CsPbCl3bulk crystal and the high toxicity of Pb2+, it is significant to explore new single crystalline lead-free perovskites with highly efficient blue light emission. Herein, two new zero-dimensional (0D) hybrid indium halides of [H2EP]2InCl6·Cl·H2O·C3H6O and [H3AEP]InCl6··H2O (EP = 1-ethylpiperazine, AEP = N-aminoethyl piperazine) were prepared. Remarkably, these 0D indium halides display unusual blue light emissions (about 430 nm) with a highest PLQY of 13.44%. To the best of our knowledge, this work represents one of the first higher energy blue light emitters in hybrid indium perovskites, which would advance the research on lead-free hybrid halides for next-generation luminescent materials.

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 (H3AEP)2CdBr6·2Br based on discrete octahedral [CdBr6]4–units. Remarkably, the bulk crystal of (H3AEP)2CdBr6·2Br 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]Cu6I8was prepared and structurally characterized with a novel three-dimensional (3D) [Cu6I8]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.

Recently, two-dimensional (2D) hybrid lead halide perovskite has been widely utilized as a preferred platform of optoelectronic material with tailorable compositions, structures, and intrinsic broadband emission properties, and this achievement significantly promotes the research desirability to explore a new type of halide prototype to mimic the 2D perovskite model. Herein, we first performed a systematic approach on one-dimensional (1D) perovskite and realized comparable performances in both structural and property modulations. Specifically, by choosing diversified organic cations as a structural design strategy, we successfully constructed a series of 1D APbBr3(A = DBU, 1,8-diazabicyclo[5.4.0]undec-7-ene; DMTHP, 5,5-dimethyl-1,4,5,6-tetrahydropyrimidine; DBN, 1,5-diazabicyclo[4.3.0]-5-nonene; EPD, 1-ethylpiperidine) homologues based on identical 1D face-shared octahedral [PbBr3]−chains. This structural model features large accommodation ability for a variety of organic blocks enabling diversified photoluminescence (PL) properties from broadband yellow to white light emissions. Most remarkably, [DBU]PbBr3displays broadband yellow (0.47, 0.45) and white (0.32, 0.36) light emissions from two excited centers corresponding to distinct self-trapped excitons (STEs). These efficient dual light emissions were verified by high photoluminescence quantum yields (PLQYs) of 5.47 and 5.17%, respectively. The multiple advantages of unified crystal lattice, tailorable chemical composition, and tunable PL performance enable this 1D APbBr3perovskite to be an emerging and standard structural prototype to diversify and optimize the optoelectronic properties with potential in single-component white-light-emitting diodes.

Commercially available rare-earth-doped inorganic oxide materials have been widely applied as X-ray scintillators, but the fragile characteristics, high detection limit, and harsh preparation condition seriously restrict their wide applications. Furthermore, it remains a huge challenge to realize X-ray flexible imaging technology for real-time monitoring of the curving interface of complex devices. To address these issues, we herein report two isostructural cuprous halides of zero-dimensional (0D) [AEPipz]CuX3·X·H2O (AEPipz = N-aminoethylpiperazine, X = Br and I) with controllable size to nanosize crystal as highly efficient scintillators toward flexible X-ray imaging. These cuprous halides exhibit highly efficient cyan photoluminescence and radioluminescence emissions with the highest quantum yield of 92.1% and light yield of 62,400 photons MeV–1, respectively, surpassing most of the commercially available inorganic scintillators. Meanwhile, the ultralow detection limit of 95.7 nGyairs–1was far below the X-ray dose required for diagnosis (5.5 μGyairs–1). More significantly, the flexible film is facilely assembled with excellent foldability and high crack resistance, which further acts as a scintillation screen achieving a high spatial resolution of 17.4 lp mm–1in X-ray imaging, demonstrating the potential application in wearable radiation radiography. The combined advantages of high light yield, low detection limit, and excellent flexibility promote these 0D cuprous halides as the most promising X-ray scintillators.

Organic-inorganic hybrid molecular fluorescent materials have attracted much attention due to their application potential in white LEDs and high-definition displays. However, achieving high thermal stability for the fields of lighting/displays remains greatly challenging based on the hybrid molecular materials. Herein, we reported a crystalline state 1D rigid rare-earth hybrid coordinate polymer molecular crystal [(CH3CH2)4N]Tb[CH2(SO3)2] (1) along with high quantum yield (QY) 75.2%. Interestingly, this hybrid molecular crystal remains stable up to 728 K (∼455 °C). Remarkably, it exhibits excellent fluorescence thermal stability at high temperatures (150 °C, >95% and 150–200 °C, >82%) and a high thermal activation energy of 568.7 meV. Besides, the fabricated n-UV chips based white-LED by 1, commercial red Y2O3:Eu3+and blue BaMgAl10O17:Eu2+phosphor emits white light with color coordinates (CIE, 0.33, 0.32), high color rendering index (CRI) of 91.2, and correlated color temperature (CCT) 5623 K. These results reveal that this ultrahigh thermal stability hybrid molecular crystal as a green phosphor has great potential applications for displays or WLEDs. Therefore, this study opens a new avenue to develop novel rare-earth phosphors and gives new visions for hybrid molecular fluorescent materials.

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, [NH4(18-Crown-6)]2MnBr4, [Ca(18-Crown-6)·3H2O](18-Crown-6)MnBr4, [NH4(dibenzo-18-Crown-6)]2MnBr4, and [Ca(dibenzo-18-Crown-6)·2H2O]MnBr4. Excited by UV light, these highly crystalline manganese halides exhibit strong green light emissions from the d–d electron transition of Mn2+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.

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 [H2BPP]Pb2X6(X = Br, 1, and Cl, 2) containing one-dimensional double [Pb2X6]2–chains using optically active 1,3-bis(4-pyridyl)-propane (BPP) as an organic cation. Under UV-light excitation, compounds 1and 2exhibit 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.

In recent years, two-dimensional (2D) hybrid lead halide perovskites based on corner-shared [PbX6] octahedrons have received extensive attention with important potentials in single-component white-light emitting diodes (WLEDs) due to the soft and distorted crystal lattices. However, limited research focused on the one-dimensional (1D) perovskites although they possess similar structural superiorities to achieve this performance. Herein, by using different types of organic amine cations as structural direction reagents, we report one new type of hybrid 1D perovskites of APbCl3(A = (DTHPE)0.5, DMTHP, DBN) based on the same 1D face-shared octahedral [PbCl3]−chains. Upon UV light excitation, these 1D APbCl3perovskites exhibit intrinsic broad-band bluish white-light emissions covering entire visible light spectra with the highest photoluminescence quantum yield (PLQY) of 6.99%, which catches up with the values of previously reported 2D perovskites. Through the systematical studies of time-resolved, temperature-dependent PL emissions, theoretical calculations, and so on, these broad-band light emissions can be ascribed to the radiative transition within conjugated organic cations. The facile assembly process, intrinsic broad-band light emissions, and high PLQYs enable these 1D APbCl3perovskites as new types of promising candidates in fabricating single-component WLEDs.

In the past few decades, organic–inorganic hybrid metal halides acting as single-component white light emission diodes (LEDs) have attracted extensive attentions, but most of the studies concentrate on the low-dimensional lead perovskites. Here, by using the nontoxic silver as optically active metal center, a series of hybrid silver halides based on one-dimensional structures were constructed and realized broadband white light emission. Compounds [H2DABCO][Ag2X4(DABCO)] (X = Br (1), I (2)) feature one-dimensional [Ag2X4(DABCO)]2–structures charged balanced by [H2DABCO]2+cations. Compound 1exhibits an efficient broadband white-light emission with photoluminescence quantum efficiency (PLQE) of about 2.1% and excellent photochemical stability, while compound 2gives a broadband yellow-white emission centered at 556 nm. [HDABCO]3Ag5Cl8(3) gives a strong broadband yellow emission (585 nm) with high PLQE of 6.7%, which can be easily fabricated as a white light emitting device. Based on the temperature-dependent, particle-size-dependent, and time-resolved PL measurements as well as other detailed studies, the broadband white-light emissions are ascribed to the synergetic effects of the organic and inorganic components. Our work provides a unique structural assembly method to explore lead-free single-component white-light illuminants from molecular level.

Visible light driven photocatalysts based on crystalline metal halides received much less attention compared with dense or composite oxide semiconductors due to low photochemical stabilities. Here, by using large conjugated organic cations as structural direction agents, a series of hybrid cuprous and/or lead halides have been solvothermally prepared and structurally characterized. Compounds H[(Me)3-TPT]6(Cu2I6)3(Pb6I19)·(H2O)2(1) and [(Me)3-TPT]2Cu2Pb3Br14(2; TPT = 2,4,6-tri(4-pyridyl)-1,3,5-triazine) contain uncommon Lindqvist-type [Pb6I19]7–nanoclusters and heterometallic [Cu2Pb3Br14]6–units, respectively. Compounds [H3TIB]2Pb5Br16(3) and H[(Me)3-TIB]2Pb5I17(4; TIB = 1,3,5-tris(1-imidazolyl)benzene) are composed of one-dimensional (1D) [Pb5Br16]6–chains and two-dimensional (2D) [Pb5I17]7–layers, respectively. The photosensitized conjugated organic cations offer a great contribution to the conduction bands, which lead to narrow band gaps of 2.01–2.35 eV. Under visible light irradiation, compound 4exhibits efficient and stable photocatalytic degradation activity for various organic pollutants. The possible photocatalytic mechanism obtained from the radical trapping experiments and electronic band structural calculation show that conjugated organic cations effectively inhibit the recombination of photoinduced electron–hole pairs leading to excellent photocatalytic activity and photochemical stability.

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

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]M8X10(M = Cu, Ag, X = Br, I). The compounds feature a three-dimensional anionic [M8X10]2–network composed of a one-dimensional [M8X12] chain based on MX4tetrahedral 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.

Multifunctional stimuli-responsive luminescent and optical switching is extremely crucial for wide advanced photonic applications, but it remains a challenging objective for halide perovskites. Herein, by performing single-crystal to single-crystal (SC–SC) transformation as a dynamic molecular strategy, we realized a reversible triple-mode photoluminescence, radioluminescence (PL and RL), and nonlinear optical (NLO) switching in a pair of zero-dimensional (0D) hybrid cuprous halides of [ETPP]2Cu4Br6and [ETPP]CuBr2. Specifically, [ETPP]2Cu4Br6and [ETPP]CuBr2display highly efficient yellow and green light emissions under UV light excitation with the highest quantum yield of up to near unity. Simultaneously, identical radioluminescence can also be activated by using X-ray as RL with a light yield of up to 57,974 photons MeV–1, surpassing most of the previously reported hybrid cuprous halides. Most remarkably, reversible SC–SC transformation between them can be realized in an ethanol impregnation-heating process, which provides reversible PL/RL transitions in two light-emitting states. Additionally, this process is also accompanied by transition between the centrosymmetric NLO-inactive [ETPP]2Cu4Br6and noncentrosymmetric NLO-active [ETPP]CuBr2through reversible second harmonic generation (SHG) “silent-active” switching. To the best of our knowledge, this is the first reported triple-mode reversible PL, RL, and SHG switching in halide perovskite chemistry, which can realize advanced applications in data storage, information security, optical logic gates, etc.

With mixed transition-metal (TM) complex, alkali-metal cations, or halogen anions as structure-directing agents, two types of two-dimensional (2D) layered inorganic–organic hybrid silver bromides were prepared and structurally characterized as K[TM(2,2-bipy)3]2Ag6Br11(TM = Ni (1), Co (2), Zn (3), Fe (4)) and [TM(2,2-bipy)3]2Ag13Br17(TM = Ni (5), Co (6), Zn (7), Fe (8)). Compounds 1–4feature 2D microporous anionic [Ag6Br11]5–layers composed of [Ag3Br7] secondary building units based on AgBr4tetrahedral units, and compounds 5–8contain 2D [Ag13Br16]3–layers built from the one-dimensional complex [Ag8Br12] and [Ag5Br8] chains. The photosensitization of TM complex dyes led to the narrow semiconducting behaviors with tunable band gaps of 1.73–2.71 eV for the title compounds, which result in excellent and stable photocatalytic degradation activities over organic pollutants under visible-light irradiation. The studies of photocatalytic mechanism based on radical-trapping experiments and electronic band structural calculation show that the TM complex cations play important roles in the photocatalytical activities and photochemical stabilities due to their excellent separating abilities for photogenerated carriers. This technique affords one new type of visible-light-driven photocatalyst and facilitates the integration of 2D layered materials and semiconducting photocatalytic properties into one hybrid d10TM halogenide.

Highly efficient and narrowband blue light-emitting performance is extremely crucial for the optoelectronic applications of organic-inorganic hybrid perovskites. However, the not yet viable approach has been shown to simultaneously improve photoluminescence quantum yield (PLQY) and narrow linewidth of blue light emission. Herein, a new crystal rigidifying strategy is proposed as a viable dual-optimization avenue. Specifically, we perform a post-synthetic technique on hybrid cadmium halides and successfully convert zero-dimensional (0D) DMP-0-CdBr4to one-dimensional (1D) DMP-1-CdBr3, accompanied by luminescent transformation from sky-blue (470 nm) to deep-blue (432 nm) emissions. The structural evolution from discrete block to infinite chain significantly enhances the crystal rigidity, which results in narrower emission linewidth (89 to 50 nm) and increased color purity (74.5% to 96.7%). Synchronously, the PLQY also realizes a notable enhancement from 14.0% to 52.3%. Systematical characterizations demonstrate that enhanced crystal rigidity simultaneously weakens the electron-phonon interaction and slows down nonradiative decay, which narrows the emission linewidth and boosts the PLQY. The highly efficient light-emitting performance enables them as excellent down-conversion blue phosphors to fabricate solid-state LED giving bright warm white light with high color rendering index of 95.4. This work paves a novel structural optimization way to rationally design or fine-tune high-performance blue-light emitting halides.

Hybrid metal halides are an emerging class of highly efficient photoluminescent (PL) materials. However, very few of them show reversible on–off PL switching under external stimuli and have the potential to perform as next-generation intelligent materials with applications in cutting-edge photoelectric devices. Herein, we report single crystal-to-single crystal (SC–SC) structural and PL transitions among three 0D hybrid antimony halides, namely, nonemissive α-[DHEP]SbCl5(1), yellow-emissive β-[DHEP]SbCl5·2H2O (2), and red-emissive β-[DHEP]SbCl5(3), by a dynamic phonon-engineering strategy. The reversible SC–SC transformation between 1and 2is triggered by acetone or methanol, affording the reversible PL on–off switching. The transition between yellow-emissive and red-emissive solids is achieved by the reversible SC–SC transformation between 2and 3through the process of removal/adsorption of guest water molecules. Meanwhile, the 3to 1transition is performed by the introduction of methanol, which is accompanied by the quenching of red emission. Therefore, a triple-mode reversible PL off–onI–onII–off switching is realized in metal halide hybrids for the first time, including the off–onI(yellow), color-tunable onI–onII(yellow-red), and onII–off (red) modes. More importantly, the reversible PL switching in 0D hybrid antimony halides make them suitable for successful applications in the protection and anti-counterfeiting of confidential information as well as in optical logic gates.

The new compounds Sc2Nb4‐xSn5(x = 0.37, 0.52), YNb6Sn6, and ErNb6Sn5are synthesized from mixtures of the elements (1000—1050 °C for 8 d, annealing at 770—850 °C for 8—10 d, 30% yield for ErNb6Sn5).

K2Mg4.72Sn3and K3Mg18Tt11(Tt: Sn, Pb) are synthesized from mixtures of the elements (800 °C for 2—3 d followed by annealing at 500—520 °C for 6—7 d) and characterized by single crystal XRD.

Tm3MnSn4.84, Tm3MnSn4.71, Lu3MnSn4.95, and Lu3MnSn4.79are prepared from the corresponding elements (Ta tubes, 1050 °C, 7 d followed by annealing at 650 °C for 15 d).

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.