Three-Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission

Considering the instability and low photoluminescence quantum yield (PLQY) of blue-emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d¹⁰ transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH₄)₂]CuPbBr₅ with new type of three-dimensional (3D) anionic framework. [(NH₄)₂]CuPbBr₅ exhibits strong band-edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH₄)₂]CuPbBr₅ also displays broadband red light emissions derived from self-trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non-perovskite bimetallic halide with highly efficient and stable blue light emission.     

Hybrid Metal Halides with Multiple Photoluminescence Centers

Very little is known about the realm of solid‐state metal halide compounds comprising two or more halometalate anions. Such compounds would be of great interest if their optical and electronic properties could be rationally designed. Herein, we report a new example of metal halide cluster‐assembled compound (C₉NH₂₀)₉[Pb₃Br₁₁](MnBr₄)₂, featuring distinctly different anionic polyhedra, namely, a rare lead halide cluster [Pb₃Br₁₁]^5? and [MnBr₄]^2?. In accordance with its multinary zero‐dimensional (0D) structure, this compound is found to contain two distinct emission centers, 565 nm and 528 nm, resulting from the formation of self‐trapped excitons and ⁴T₁‐⁶A₁ transition of Mn²⁺ ions, respectively. Based on the high durability of (C₉NH₂₀)₉[Pb₃Br₁₁](MnBr₄)₂ upon light and heat, as well as high photoluminescence quantum yield (PLQY) of 49.8 % under 450 nm blue light excitation, white light‐emitting diodes (WLEDs) are fabricated, showcasing its potential in backlight application.     

Pressure‐Induced Emission (PIE) and Phase Transition of a Two‐dimensional Halide Double Perovskite (BA)4AgBiBr8 (BA=CH3(CH2)3NH3+)

Two‐dimensional (2D) halide perovskites have attracted significant attention due to their compositional flexibility and electronic diversity. Understanding the structure–property relationships in 2D double perovskites is essential for their development for optoelectronic applications. In this work, we observed the emergence of pressure‐induced emission (PIE) at 2.5 GPa with a broad emission band and large Stokes shift from initially nonfluorescent (BA)₄AgBiBr₈ (BA=CH₃(CH₂)₃NH₃⁺). The emission intensity increased significantly upon further compression up to 8.2 GPa. Moreover, the band gap narrowed from the starting 2.61 eV to 2.19 eV at 25.0 GPa accompanied by a color change from light yellow to dark yellow. Analysis of combined in situ high‐pressure photoluminescence, absorption, and angle‐dispersive X‐ray diffraction data indicates that the observed PIE can be attributed to the emission from self‐trapped excitons. This coincides with [AgBr₆]^5? and [BiBr₆]^3? inter‐octahedral tilting which cause a structural phase transition. High‐pressure study on (BA)₄AgBiBr₈ sheds light on the relationship between the structure and optical properties that may improve the material's potential applications in the fields of pressure sensing, information storage and trademark security.     

Ultra‐Narrow‐Band Blue‐Emitting Oxoberyllates AELi2[Be4O6]:Eu2+ (AE=Sr,Ba) Paving the Way to Efficient RGB pc‐LEDs

Highly efficient phosphor‐converted light‐emitting diodes (pc‐LEDs) are popular in lighting and high‐tech electronics applications. The main goals of present LED research are increasing light quality, preserving color point stability and reducing energy consumption. For those purposes excellent phosphors in all spectral regions are required. Here, we report on ultra‐narrow band blue emitting oxoberyllates AELi₂[Be₄O₆]:Eu²⁺ (AE=Sr,Ba) exhibiting a rigid covalent network isotypic to the nitridoalumosilicate BaLi₂[(Al₂Si₂)N₆]:Eu²⁺. The oxoberyllates’ extremely small Stokes shift and unprecedented ultra‐narrow band blue emission with fwhm ≈25 nm (≈1200 cm^?1) at λ_em=454–456 nm result from its rigid, highly condensed tetrahedra network. AELi₂[Be₄O₆]:Eu²⁺ allows for using short‐wavelength blue LEDs (λ_em<440 nm) for efficient excitation of the ultra‐narrow band blue phosphor, for application in violet pumped white RGB phosphor LEDs with improved color point stability, excellent color rendering, and high energy efficiency.     

Air‐Stable,Lead‐Free Zero‐Dimensional Mixed Bismuth‐Antimony Perovskite Single Crystals with Ultra‐broadband Emission

Lead‐free zero‐dimensional (0D) organic‐inorganic metal halide perovskites have recently attracted increasing attention for their excellent photoluminescence properties and chemical stability. Here, we report the synthesis and characterization of an air‐stable 0D mixed metal halide perovskite (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O, in which individual [BiBr₆]^3? and [SbBr₆]^3? octahedral units are completely isolated and surrounded by the large organic cation C₈H₁₂N⁺. Upon photoexcitation, the bulk crystals exhibit ultra‐broadband emission ranging from 400 to 850 nm, which originates from both free excitons and self‐trapped excitons. This is the first example of 0D perovskites with broadband emission spanning the entire visible spectrum. In addition, (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O exhibits excellent humidity and light stability. These findings present a new direction towards the design of environmentally‐friendly, high‐performance 0D perovskite light emitters.     

Air‐Stable,Lead‐Free Zero‐Dimensional Mixed Bismuth‐Antimony Perovskite Single Crystals with Ultra‐broadband Emission

Lead‐free zero‐dimensional (0D) organic‐inorganic metal halide perovskites have recently attracted increasing attention for their excellent photoluminescence properties and chemical stability. Here, we report the synthesis and characterization of an air‐stable 0D mixed metal halide perovskite (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O, in which individual [BiBr₆]^3? and [SbBr₆]^3? octahedral units are completely isolated and surrounded by the large organic cation C₈H₁₂N⁺. Upon photoexcitation, the bulk crystals exhibit ultra‐broadband emission ranging from 400 to 850 nm, which originates from both free excitons and self‐trapped excitons. This is the first example of 0D perovskites with broadband emission spanning the entire visible spectrum. In addition, (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O exhibits excellent humidity and light stability. These findings present a new direction towards the design of environmentally‐friendly, high‐performance 0D perovskite light emitters.     

Crystal rigidifying strategy toward hybrid cadmium halide to achieve highly efficient and narrowband blue light emission

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-CdBr₄ to 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.     

Top‐Down Fabrication of Stable Methylammonium Lead Halide Perovskite Nanocrystals by Employing a Mixture of Ligands as Coordinating Solvents

A top‐down method is demonstrated for the fabrication of CH₃NH₃PbBr₃ and CH₃NH₃PbI₃ perovskite nanocrystals, employing a mixture of ligands oleic acid and oleylamine as coordinating solvents. This approach avoids the use of any polar solvents, skips multiple reaction steps by employing a simple ultrasonic treatment of the perovskite precursors, and yields rather monodisperse blue‐, green‐, and red‐emitting methylammonium lead halide nanocrystals with a high photoluminescence quantum yield (up to 72 % for the green‐emitting nanocrystals) and remarkably improved stability. After discussing all relevant reaction parameters, the green‐emitting CH₃NH₃PbBr₃ nanocrystals are employed as a component of down‐conversion white‐light‐emitting devices_.     

A Novel trans‐1‐(9‐Anthryl)‐2‐phenylethene Derivative Containing a Phenanthroimidazole Unit for Application in Organic Light‐Emitting Diodes

Aryl‐substituted phenanthroimidazoles (PIs) have attracted tremendous attention in the field of organic light‐emitting diodes (OLEDs), because they are simple to synthesize and have excellent thermal properties, high photoluminescence quantum yields (PLQYs), and bipolar properties. Herein, a novel blue–green emitting material, (E)‐2‐{4′‐[2‐(anthracen‐9‐yl)vinyl]‐[1,1′‐biphenyl]‐4‐yl}‐1‐phenyl‐1H‐phenanthro[9,10‐d]imidazole (APE‐PPI), containing a t‐APE [1‐(9‐anthryl)‐2‐phenylethene] core and a PI moiety was designed and synthesized. Owing to the PI skeleton, APE‐PPI possesses high thermal stability and a high PLQY, and the compound exhibits bipolar transporting characteristics, which were identified by single‐carrier devices. Nondoped blue–green OLEDs with APE‐PPI as the emitting layer show emission at λ=508 nm, a full width at half maximum of 82 nm, a maximum brightness of 9042 cd m^?2, a maximum current efficiency of 2.14 cd A^?1, and Commission Internationale de L'Eclairage (CIE) coordinates of (0.26, 0.55). Furthermore, a white OLED (WOLED) was fabricated by employing APE‐PPI as the blue–green emitting layer and 4‐(dicyanomethylene)‐2‐tert‐butyl‐6‐(1,1,7,7‐tetramethyljulolidin‐4‐yl‐vinyl)‐4H‐pyran (DCJTB) doped in tris‐(8‐hydroxyquinolinato)aluminum (Alq₃) as the red–green emitting layer. This WOLED exhibited a maximum brightness of 10029 cd m^?2, a maximum current efficiency of 16.05 cd A^?1, CIE coordinates of (0.47, 0.47), and a color rendering index (CRI) of 85. The high performance of APE‐PPI‐based devices suggests that the t‐APE and PI combination can potentially be used to synthesize efficient electroluminescent materials for WOLEDs.     

Controlling the White‐Light Generation of [(RSn)4E6]: Effects of Substituent and Chalcogenide Variation

Adamantane‐type organotin chalcogenide clusters of the general composition [(RT)₄S₆] (R=aromatic substituent, T=Si, Ge, Sn) have extreme non‐linear optical properties that lead to highly directional white‐light generation (WLG) upon irradiation with an IR laser diode. However, the mechanism is not yet understood. Now, a series of compounds [(RSn)₄E₆] (R=phenyl, cyclopentadienyl, cyclohexyl, benzyl, CH₂CH₂(C₆H₄)CO₂Et; E=S, Se), were prepared, characterized, and investigated for their nonlinear optical properties. With the exception of crystalline [(BnSn)₄S₆], all these compounds exhibit WLG with similar emission spectra; slight blue‐shifts are observed by introduction of cyclopentadienyl substituents, while the introduction of Se in the inorganic core can provoke a red‐shift. These investigations disprove the initial assumption of an aromatic substituent being a necessary precondition; the precondition seems to be the presence of (cyclic) substituents providing enough electron density.     

Werner transition‐metal complex (WTMC)‐mediated mild and efficient chemo‐selective acylation of phenols and anilines under solvent‐free condition

Werner‐type transition‐metal complexes (WTMC) such as [Co(NH₃)₅Cl]Cl₂, Cu[(NH₃)₄]SO₄, Mn(acac)₃, Ni[(NH₃)₆]Cl₂, Ni[(en)₃]S₂O₃, and Hg[Co(SCN)₄] efficiently promote the chemoselective acetylation of phenols and anilines under solvent‐free condition. The results of this study clearly shows that the optimal condition for the acetylation of anilines/phenols (1 mmol) ( 2a–r ) with acetic anhydride (1.2 mmol) in the presence of WTMC (1 mmol) and two drops of H₃PO₄ on heating for 10 min under solvent‐free condition gives the corresponding acetanilides/phenyl acetate ( 3a–r ) in good to excellent yield. Furthermore, the method is simple, efficient, chemoselective, and eco‐friendly under solvent‐free condition for the acetylation of anilines and phenols promoted by WTMC by using acetic anhydrate as the acetylating agent. The simple preparation of the catalyst, easy procedure of the acetylation reaction, and simple work‐up indicate the importance of WTMC for such reactions.     

An Efficient Synthesis and Fluorescent Properties of Pyrazole[3,4‐b]thieno[2,3‐e]pyridine Derivatives

A simple and efficient method for the synthesis of pyrazole[3,4‐b]thieno[2,3‐e]pyridine derivatives via the sequence of three‐component, catalyst‐free, and solvent‐free condensation and oxidation was described. The products feature a donor‐π‐conjugated acceptor fluorescent activity system, and the fluorescence emission wavelength was measured in methanol. Some products were fluorescent in solution emitting at blue light (λ_em = 430–505 nm).     

Concise Synthesis and Two‐Photon‐Excited Deep‐Blue Emission of 1,8‐Diazapyrenes

Efficient violet–blue‐emitting molecules are especially useful for applications in full‐color displays, solid‐state lighting, as well as in two‐photon absorption (TPA) excited frequency‐upconverted violet–blue lasing. However, the reported violet–blue‐emitting molecules generally possess small TPA cross sections. In this work, new 1,8‐diazapyrenes derivatives 3 with blue two‐photon‐excited fluorescence emission were concisely synthesized by the coupling reaction of readily available 1,4‐naphthoquinone O,O‐diacetyl dioxime ( 1 ) with internal alkynes 2 under the [{RhCl₂Cp*}₂]–Cu(OAc)₂ (Cp*=pentamethylcyclopentadienyl ligand) bimetallic catalytic system. Elongation of the π‐conjugated length of 1,8‐diazapyrenes 3 led to the increase of TPA cross sections without the expense of a redshift of the emission wavelength, probably due to the rigid planar structure of chromophores. It is especially noteworthy that 2,3,6,7‐tetra(4‐bromophenyl)‐1,8‐diazapyrene ( 3c ) has a larger TPA cross section than those of other molecules reported so far. These experimental results are explained in terms of the effects of extension of the π‐conjugated system, intramolecular charge transfer, and reduced detuning energy.     

Highly Luminescent and Ultrastable CsPbBr3 Perovskite Quantum Dots Incorporated into a Silica/Alumina Monolith

We successfully prepared QDs incorporated into a silica/alumina monolith (QDs‐SAM) by a simple sol–gel reaction of an Al–Si single precursor with CsPbBr₃ QDs blended in toluene solution, without adding water and catalyst. The resultant transparent monolith exhibits high photoluminescence quantum yields (PLQY) up to 90 %, and good photostability under strong illumination of blue light for 300 h. We show that the preliminary ligand exchange of didodecyl dimethyl ammonium bromide (DDAB) was very important to protect CsPbBr₃ QDs from surface damages during the sol–gel reaction, which not only allowed us to maintain the original optical properties of CsPbBr₃ QDs but also prevented the aggregation of QDs and made the monolith transparent. The CsPbBr₃ QDs‐SAM in powder form was easily mixed into the resins and applied as color‐converting layer with curing on blue light‐emitting diodes (LED). The material showed a high luminous efficacy of 80 lm W⁻¹ and a narrow emission with a full width at half maximum (FWHM) of 25 nm.     

Yellow-green luminescence and extreme thermal quenching in the Sr6M2Al4O15:Eu2+ (M = Y,Lu, Sc) phosphor series

A series of Eu²⁺-substituted yellow-green emitting phosphors based on the compound, Sr₆M₂Al₄O₁₅ (M = Y, Lu, Sc) were identified as potential efficient phosphors based on their high calculated Debye temperatures (Θ_D > 450 K), which acts as a proxy for photoluminescent quantum yield (PLQY). The crystal structure contains corner-sharing [MO₆] octahedra and [AlO₄] tetrahedra leading to a highly connected, densely packed crystal structure. However, contrary to prediction, these compounds all showed a low PLQY (<6.5%) at room temperature. Temperature dependent luminescence measurements indicate that the photoluminescence is intense at 80 K but loses ≈90% of the emission intensity by room temperature, with the thermal quenching temperature (T₅₀) occurring well below room temperature. These results suggest that even though Debye temperature (Θ_D) is a valid proxy for PLQY, it does not describe thermal quenching.     

Isocyanide complexes of molybdenum nitrosyl

Reaction of π-cyclopentadienylmolybdenum nitrosyl halide with CNR (R = alkyl) gives [(π-C₅H₅)Mo(NO)X₂(CNR)] (X = Br or I), [Mo(NO)(CNR)₅]X (X = I or PF₆) and [Mo(NO)(CNR)₄I]; treatment of [Mo(NO)(CNR)₅]I with R′NH₂ gives [Mo(NO)(CNR)₄ {C(NHR)(NHR′)}]I or [Mo(NO)(CNR)₄(NH₂R′)]I (R′ = alkyl) depending on temperature.     

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

Recently, low‐dimensional organic‐inorganic hybrid metal halide perovskites acting as single‐component white‐light emitting materials have attracted extensive attention, but most studies concentrate on hybrid lead perovskites. Herein, we present two isomorphic zero‐dimensional (0D) hybrid cadmium perovskites, (HMEDA)CdX₄ (HMEDA=hexamethylenediamine, X=Cl ( 1 ), Br ( 2 )), which contain isolated [CdX₄]^2? anions separated by [HMEDA]²⁺ cations. Under UV light excitation, both compounds display broadband bluish white‐light emission (515 nm for 1 and 445 nm for 2 ) covering the entire visible light spectrum with sufficient photophysical stabilities. Remarkably, compound 2 shows a high color rendering index (CRI) of 83 enabling it as a promising candidate for single‐component WLED applications. Based on the temperature‐dependent, powder‐dependent and time‐resolved PL measurements as well as other detailed studies, the broadband light emissions are attributed to self‐trapped excitons stemming from the strong electron‐phonon coupling.     

Synthesis and Physicochemical Characteristics of New Tetrachloroferrates(III) with Dimethylammonium Cation: X‐ray Crystal Structure of Bis(dimethylammonium) Chloride Tetrachloroferrate(III)

Two new tetrachloroferrates(III) have been synthesized of molecular formulas [(CH₃)₂NH₂][FeCl₄] and [(CH₃)₂NH₂]₂FeCl₅. The differences in their physicochemical properties have been highlighted using thermal analysis (TG‐MS) and differential scanning calorimetry (DSC). The crystal and molecular structure of [(CH₃)₂NH]₂FeCl₅ was determined. The iron(III) cation is four coordinated by chloride ions, and it adopts a slightly distorted tetrahedral coordination with three angles smaller and three larger than the tetrahedral one. In the structure four intermolecular N‐H···Cl hydrogen bonds link the [(CH₃)₂NH₂]⁺ cations to dimers via a Cl^? bridge.     

A two‐dimensional organic–inorganic hybrid perovskite‐type semiconductor: poly[(2‐azaniumylethyl)trimethylphosphanium [tetra‐μ‐bromido‐plumbate(II)]]

Recently, with the prevalence of `perovskite fever', organic–inorganic hybrid perovskites (OHPs) have attracted intense attention due to their remarkable structural variability and highly tunable properties. In particular, the optical and electrical properties of organic–inorganic hybrid lead halides are typical of the OHP family. Besides, although three‐dimensional hybrid perovskites, such as [CH₃NH₃]PbX₃ (X = Cl, Br or I), have been reported, the development of new organic–inorganic hybrid semiconductors is still an area in urgent need of exploration. Here, an organic–inorganic hybrid lead halide perovskite is reported, namely poly[(2‐azaniumylethyl)trimethylphosphanium [tetra‐μ‐bromido‐plumbate(II)]], {(C₅H₁₆NP)[PbBr₄]}_n, in which an organic cation is embedded in inorganic two‐dimensional (2D) mesh layers to produce a sandwich structure. This unique sandwich 2D hybrid perovskite material shows an indirect band gap of ～2.700 eV. The properties of this compound as a semiconductor are demonstrated by a series of optical characterizations and indicate potential applications for optical devices.     

Heteronukleare Komplexverbindungen mit Metall—Metall-Bindungen. IX [1]. Amin-kupfer(I)-carbonylmetallate mit Cobalt,Eisen oder Mangan

Heteronuclear Coordination Compounds with Metal—Metal Bonds. IX. Amine Copper(I) Carbonyl Metalates with Cobalt, Iron, or Manganese Colourless crystals of the carbonyl copper complex [(NH₃)₃(CO)Cu][Co(CO)₄] ( 1 a ) are formed in the reaction of [Cu(NH₃)₄]Cl and Na[Co(CO)₄] (T < ? 8°C, p_CO = 1 bar); above ?5°C and under N₂-atmosphere 1 a converts to [(NH₃)₂CuCo(CO)₄] ( C ), which serves as a starting material for the synthesis of new copper cobaltates: the amines N-amino piperidine, N,N-dimethyl ethylenediamine (dmed) and N-benzyl N,N′-dimethyl ethylenediamine (bn-dmed) replace NH₃ to form [(C₅H₁₀N? NH₂)₃CuCo(CO)₄] ( 1 b ), [(dmed)CuCo(CO)₄] ( 1 c ), [(bn-dmed)CuCo(CO)₄] ( 1 d ) the Cu? Co-bond remaining intact. [(NH₃)₂CuFe(CO)₃NO] ( 2 a ) is isosteric with C ; it is synthesized from [Cu(NH₃)₄]Cl and Na[Fe(CO)₃NO] in aqueous solution; 2 a reacts with N,N,N′,N′-tetramethyl ethylenediamine (tmed) to form [(tmed)(NH₃)CuFe(CO)₃NO] ( 2b ). The [Mn(CO)₅]^? ion reacts with ammine copper ions to form the tetranuclear cluster [{(NH₃)CuMn(CO)₅}₂] ( 3 ). All new compounds have been investigated by X-ray structure analysis.