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Inorganic zeolites have excellent molecular sieving properties, but they are difficult to process into macroscopic structures. In this work, we use metal–organic framework (MOF) glass as substrates to engineer the interface with inorganic zeolites, and then assemble the discrete crystalline zeolite powders into monolithic structures. The zeolites are well dispersed and stabilized within the MOF glass matrix, and the monolith has satisfactory mechanical stabilities for membrane applications. We demonstrate the effective separation performance of the membrane for 1,3‐butadiene (C4H6) from other C4 hydrocarbons, which is a crucial and challenging separation in the chemical industry. The membrane achieves a high permeance of C4H6 (693.00±21.83 GPU) and a high selectivity over n‐butene, n‐butane, isobutene, and isobutane (9.72, 9.94, 10.31, and 11.94, respectively). This strategy opens up new possibilities for developing advanced membrane materials for difficult hydrocarbon separations. [ABSTRACT FROM AUTHOR]

Quantum dots (QDs) with non‐blinking applied in bio‐imaging is important for understanding cellular dynamics by monitoring single particles in living cells. Antibunching is once believed to be applied to identify a single QD, which shows a strong dependence on the atom or ion number. However, recent works indicate that the antibunching alone may not be sufficient to demonstrate that the fluorescence comes from a single QD. To some extent, it is neither necessary nor sufficient for a single QD, though it is absolutely right for a single atom because a single QD is composed of thousands of atoms, which in principle are favorable to the formation of multi‐excitonic states. Blinking behavior, almost unobservable in ensembles due to the averaging, is characteristic of the single QD which owns the quantum effect due to its discrete energy levels. Here, a method of transformation of a single graphene quantum dot from non‐blinking to blinking via catalytic reaction to identify a single QD is reported, which can also help with understanding the catalytic dynamics of a single QD, which is a complementary means of confirming a single QD. The reported technique paves the way to understanding a single QD and its catalytic and kinetic behaviors. [ABSTRACT FROM AUTHOR]

Halide double perovskites [A2MIMIIIX6] are an important class of materials that have garnered substantial interest as non‐toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs2NaLnI6 (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported. [ABSTRACT FROM AUTHOR]

Here, we report kinetic studies using electron spin resonance spectroscopy on spin catalysis reactions caused by using graphene belts which were synthesized by a radical coupling method. The results show that σ‐type free radical species provide the dominant sites for catalytic activity through the spin‐spin interaction, although there are some other influencing factors. The spin catalysis mechanism can be applied both in the oxygen reduction reaction (ORR) and in organic synthesis. The graphene belt spin catalyst shows excellent performance with a high ORR half‐wave potential of 0.81 V and long‐term stability with almost no loss of activity after 50 000 cycles in alkaline media. It also shows excellent performance in a benzylamine coupling with molecular oxygen to generate the corresponding imine at an average conversion of ≈97.7 % and an average yield of ≈97.9 %. This work opens up a new research direction for understanding aerobic processes in the field of spin catalysis. [ABSTRACT FROM AUTHOR]

Chiral hybrid metal halides with a high dissymmetry factor (glum) and a superior photoluminescence quantum yield (PLQY) are promising candidates for circularly polarized luminescence (CPL) light sources. Here, we report eight new chiral hybrid manganese halides, crystallizing in the non‐centrosymmetric space group P212121 and showing intense CPL emissions. Oppositely‐signed circular dichroism (CD) and CPL signals are detected according to the R‐ and S‐configurations of the chiral alkanolammonium cations. Time‐resolved PL spectra show long averaged decay lifetimes up to 1 ms for (R‐3‐quinuclidinol)MnBr3 (R‐1). The glum of polycrystalline samples for coordinated structures (23×10−3) is more than doubled compared with the non‐coordinated ones (8.5×10−3), due to the structural variations. R‐1 exhibit both a high glum and a high PLQY (50.2 %). The effective chirality transfer mechanism through coordination bonds, with strongly emissive MnII centers, enables a new class of high‐performance CPL materials. [ABSTRACT FROM AUTHOR]

Vacancy‐ordered double perovskites are attracting significant attention due to their chemical diversity and interesting optoelectronic properties. With a view to understanding both the optical and magnetic properties of these compounds, two series of RuIV halides are presented; A2RuCl6 and A2RuBr6, where A is K, NH4, Rb or Cs. We show that the optical properties and spin‐orbit coupling (SOC) behavior can be tuned through changing the A cation and the halide. Within a series, the energy of the ligand‐to‐metal charge transfer increases as the unit cell expands with the larger A cation, and the band gaps are higher for the respective chlorides than for the bromides. The magnetic moments of the systems are temperature dependent due to a non‐magnetic ground state with Jeff=0 caused by SOC. Ru‐X covalency, and consequently, the delocalization of metal d‐electrons, result in systematic trends of the SOC constants due to variations in the A cation and the halide anion. [ABSTRACT FROM AUTHOR]

Although metal–organic frameworks (MOFs) are being widely used to derive functional nanomaterials through pyrolysis, the actual mechanisms involved remain unclear. In the limited studies to date, elemental metallic species are found to be the initial products, which limits the variety of MOF‐derived nanomaterials. Here, the pyrolysis of a manganese triazolate MOF is examined carefully in terms of phase transformation, reaction pathways, and morphology evolution in different conditions. Surprisingly, the formation of metal is not detected when manganese triazolate is pyrolyzed in an oxygen‐free environment. Instead, a direct transformation into nanoparticles of manganese nitride, Mn2Nx embedded in N‐doped graphitic carbon took place. The electrically conductive Mn2Nx nanoparticles show much better air stability than bulk samples and exhibit promising electrocatalytic performance for the oxygen reduction reaction. The findings on pyrolysis mechanisms expand the potential of MOF as a precursor to derive more functional nanomaterials. [ABSTRACT FROM AUTHOR]

This Review examines how the intermarriage of perovskite and metal‐organic framework crystals brings new paradigms for material design and functionality. The strategic combination of halide perovskites and metal–organic frameworks (MOFs) has generated a new family of porous composite materials that will enable new applications, including optoelectronic, catalysis, sensing, and data encryption. This Review surveys the current progress of this exciting new area. Fundamental aspects, including perovskite nucleation and growth, heterojunction electron–hole transfer, electronic structure, and luminescence within confined spaces, are highlighted, with suggestions of approaches by which guest confinement within MOFs can be synthetically designed. We further address the underlying principles and discuss the new insights and tools for the manipulation of these composite materials for the development of synthetic microporous semiconducting composites, as well as new strategies for host–guest interfacial engineering. [ABSTRACT FROM AUTHOR]

There has been a great deal of recent interest in extended compounds containing Ru3+ and Ru4+ in light of their range of unusual physical properties. Many of these properties are displayed in compounds with the perovskite and related structures. Here we report an array of structurally diverse hybrid ruthenium halide perovskites and related compounds: MA2RuX6 (X=Cl or Br), MA2MRuX6 (M=Na, K or Ag; X=Cl or Br) and MA3Ru2X9 (X=Br) based upon the use of methylammonium (MA=CH3NH3+) on the perovskite A site. The compounds MA2RuX6 with Ru4+ crystallize in the trigonal space group R3‾m and can be described as vacancy‐ordered double‐perovskites. The ordered compounds MA2MRuX6 with M+ and Ru3+ crystallize in a structure related to BaNiO3 with alternating MX6 and RuX6 face‐shared octahedra forming linear chains in the trigonal P3‾m space group. The compound MA3Ru2Br9 crystallizes in the orthorhombic Cmcm space group and displays pairs of face‐sharing octahedra forming isolated Ru2Br9 moieties with very short Ru–Ru contacts of 2.789 Å. The structural details, including the role of hydrogen bonding and dimensionality, as well as the optical and magnetic properties of these compounds are described. The magnetic behavior of all three classes of compounds is influenced by spin–orbit coupling and their temperature‐dependent behavior has been compared with the predictions of the appropriate Kotani models. [ABSTRACT FROM AUTHOR]

Abstract: Following the recent discovery of a new family of hybrid ABX3 perovskites where X=(H2POO)− (hypophosphite), this work reports a facile synthesis for mixed X‐site formate perovskites of composition [GUA]Mn(HCOO)3−x(H2POO)x, with two crystallographically distinct, partially ordered intermediate phases with x=0.84 and 1.53, corresponding to ca. 30 and 50 mol % hypophosphite, respectively. These phases are characterised by single‐crystal XRD and solid‐state NMR spectroscopy, and their magnetic properties are reported. [ABSTRACT FROM AUTHOR]

Abstract: There is current interest in finding nontoxic alternatives to lead‐halide perovskites for optoelectronic applications. Silver–bismuth double perovskites have recently gained attention, but evaluating their carrier lifetime and recombination mechanisms from photoluminescence measurements is challenging due to their indirect bandgap. In this work, transient absorption spectroscopy is used to directly track the photocarrier population in Cs2AgBiBr6 by measuring the ground state bleach dynamics. A small initial drop is resolved in the ground state bleach on a picosecond timescale, after which the remaining photocarriers decay monoexponentially with a lifetime of 1.4 µs. The majority of the early‐time decay is attributed to hot‐carrier thermalization from the direct transition to the indirect bandgap, and the 1.4 µs lifetime represents the recombination of most photocarriers. From this lifetime, a steady‐state excess carrier density of 2.2 × 1016 cm−3 under 1 sun is calculated, which is an order of magnitude larger than that for methylammonium lead iodide, suggesting that charge transport and extraction can be efficient in Cs2AgBiBr6 solar cells. [ABSTRACT FROM AUTHOR]

Abstract: The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first‐order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low‐ and high‐temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals. [ABSTRACT FROM AUTHOR]

The mechanical properties of formamidinium lead halide perovskites (FAPbX3, X=Br or I) grown by inverse-temperature crystallization have been studied by nanoindentation. The measured Young's moduli (9.7-12.3 GPa) and hardnesses (0.36-0.45 GPa) indicate good mechanical flexibility and ductility. The effects of hydrogen bonding were evaluated by performing ab initio molecular dynamics on both formamidinium and methylammonium perovskites and calculating radial distribution functions. The structural and chemical factors influencing these properties are discussed by comparison with corresponding values in the literature for other hybrid perovskites, including double perovskites. Our results reveal that bonding in the inorganic framework and hydrogen bonding play important roles in determining elastic stiffness. The influence of the organic cation becomes more important for structures at the limit of their perovskite stability, indicated by high tolerance factors. [ABSTRACT FROM AUTHOR]

The formation of two-dimensional (2D) oriented porous organic cage crystals (consisting of imine-based tetrahedral molecules) on various substrates (such as silicon wafers and glass) by solution-processing is reported. Insight into the crystallinity, preferred orientation, and cage crystal growth was obtained by experimental and computational techniques. For the first time, structural defects in porous molecular materials were observed directly and the defect concentration could be correlated with crystal growth rate. These oriented crystals suggest potential for future applications, such as solution-processable molecular crystalline 2D membranes for molecular separations. [ABSTRACT FROM AUTHOR]

Understanding the driving forces controlling crystallization is essential for the efficient synthesis and design of new materials, particularly metal-organic frameworks (MOFs), where mild solvothermal synthesis often allows access to various phases from the same reagents. Using high-energy in situ synchrotron X-ray powder diffraction, we monitor the crystallization of lithium tartrate MOFs, observing the successive crystallization and dissolution of three competing phases in one reaction. By determining rate constants and activation energies, we fully quantify the reaction energy landscape, gaining important predictive power for the choice of reaction conditions. Different reaction rates are explained by the structural relationships between the products and the reactants; larger changes in conformation result in higher activation energies. The methods we demonstrate can easily be applied to other materials, opening the door to a greater understanding of crystallization in general. [ABSTRACT FROM AUTHOR]

Desolvated zeolitic imidazolate framework ZIF-4(Zn) undergoes a discontinuous porous to dense phase transition on cooling through 140 K, with a 23 % contraction in unit cell volume. The structure of the non-porous, low temperature phase was determined from synchrotron X-ray powder diffraction data and its density was found to be slightly less than that of the densest ZIF phase, ZIF-zni. The mechanism of the phase transition involves a cooperative rotation of imidazolate linkers resulting in isotropic framework contraction and pore space minimization. DFT calculations established the energy of the new structure relative to those of the room temperature phase and ZIF-zni, while DSC measurements indicate the entropic stabilization of the porous room temperature phase at temperatures above 140 K. [ABSTRACT FROM AUTHOR]

The structural and electronic properties of MnB4 were studied by high-temperature powder X-ray diffraction and measurements of the conductivity and Seebeck coefficient on spark-plasma-sintered samples. A transition from the room-temperature monoclinic structure (space group P21/ c) to a high-temperature orthorhombic structure (space group Pnnm) was observed at about 650 K. The material remained semiconducting after the transition, but its behavior changed from p-type to n-type. 55Mn NMR measurements revealed an isotropic chemical shift of −1315 ppm, confirming an oxidation state of Mn close to I. Solid solutions of Cr1− xMn xB4 (two phases in space groups Pnnm and P21/ c) were synthesized for the first time. In addition, nanoindentation studies yielded values of (496±26) and (25.3±1.7) GPa for the Young's modulus and hardness, respectively, compared to values of 530 and 37 GPa obtained by DFT calculations. [ABSTRACT FROM AUTHOR]

Pressure-induced phase transformations (PIPTs) occur in a wide range of materials. In general, the bonding characteristics, before and after the PIPT, remain invariant in most materials, and the bond rearrangement is usually irreversible due to the strain induced under pressure. A reversible PIPT associated with a substantial bond rearrangement has been found in a metal-organic framework material, namely [tmenH2][Er(HCOO)4]2 (tmenH22+= N, N, N′, N′-tetramethylethylenediammonium). The transition is first-order and is accompanied by a unit cell volume change of about 10 %. High-pressure single-crystal X-ray diffraction studies reveal the complex bond rearrangement through the transition. The reversible nature of the transition is confirmed by means of independent nanoindentation measurements on single crystals. [ABSTRACT FROM AUTHOR]

The I2-sorption and -retention properties of several existing zeolitic imidazolate frameworks (ZIF-4, -8, -69) and a novel framework, ZIF-mnIm ([Zn(mnIm)2]; mnIm=4-methyl-5-nitroimidazolate), have been characterised using microanalysis, thermogravimetric analysis and X-ray diffraction. The topologically identical ZIF-8 ([Zn(mIm)2]; mIm=2-methylimidazolate) and ZIF-mnIm display similar sorption abilities, though strikingly different guest-retention behaviour upon heating. We discover that this guest retention is greatly enhanced upon facile amorphisation by ball milling, particularly in the case of ZIF-mnIm, for which I2 loss is retarded by as much as 200 °C. It is anticipated that this general approach should be applicable to the wide range of available metal-organic framework-type materials for the permanent storage of harmful guest species. [ABSTRACT FROM AUTHOR]

Feste Lösungen können aus anorganisch ‐ organischen Gerüsten mit dreidimensionalen Li ‐ O ‐ Li ‐ Verknüpfungen mithilfe von mechanochemischer Synthese hergestellt werden. Anhand von hochauflösender Synchroton ‐ Röntgen ‐ Pulverdiffraktometrie und Festphasen ‐ NMR ‐ Spektroskopie wurde vollständige Ligandenvermischung für die binären und ternären Systeme gezeigt (Tendenzen des Elementarzellvolumens (V) des ternären Systems {Li2(suc)x(mal)y(met)z}n im Bild). [ABSTRACT FROM AUTHOR]

Here, we report curvature‐induced electron spin catalysis by using solid carbon spheres as catalysts, which were synthesized using positive curvature molecular hexabromocyclopentadiene as a precursor molecule, following a radical coupling mechanism. The curvature spin of carbon is regarded as an overlapping state of σ‐ and π‐radical, which is identified by the inverse Laplace transform of pulse‐electron paramagnetic resonance. The growth mechanism of carbon spheres abiding by Kroto's model, is supported by the density functional theory study of thermodynamics and kinetics calculations. The solid carbon spheres present excellent catalytic behaviour of oxidation coupling of amines to form corresponding imines with the conversion of >99 %, selectivity of 98.7 %, and yield of 97.7 %, which is attributed to the predominantly curvature‐induced electron spin catalysis of carbon, supported by the calculation of oxygen adsorption energy. This work proposes a view of curvature‐induced spin catalysis of carbon, which opens up a research direction for curvature‐induced electron spin catalysis. [ABSTRACT FROM AUTHOR]

Keywords: double perovskites; Kotani model; lead-free perovskites; magnetic properties; ruthenium halides EN double perovskites Kotani model lead-free perovskites magnetic properties ruthenium halides 1 1 1 05/27/20 20200602 NES 200602 B Perowskite b Im Forschungsartikel auf S. 9059 berichten R. Seshadri, A. K.Cheetham et al. über die Synthese, Kristallstrukturen und physikalischen Eigenschaften von drei neuen Familien strukturell diverser Methylammoniumrutheniumhalogenid-Perowskiten. Double perovskites, Kotani model, lead-free perovskites, magnetic properties, ruthenium halides. [Extracted from the article]