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Hydrogel flexible sensors are widely used in wearable devices, health care, intelligent robots and other fields due to their excellent flexibility, biocompatibility and high sensitivity. With the development of single sensor to multi‐channel and multi‐mode sensor network, the sensor data also presents the characteristics of multi‐dimension, complex and massive. Traditional data analysis methods can no longer meet the data analysis requirements of hydrogel flexible sensor networks. The introduction of machine learning (ML) technology optimizes the process of data analysis. With the continuous development of multi‐layer neural network technology and the improvement of computer performance, deep learning (DL) algorithm is increasingly used to achieve higher efficiency and accuracy, provides a powerful tool for data analysis of hydrogel flexible sensor, and accelerates the intelligent process of hydrogel flexible sensor equipment. This paper introduces the classification of hydrogel flexible sensors and the working mechanism and common algorithms of ML, and summarizes the application of ML technology to assist hydrogel flexible sensors in data analysis in the fields of health care and information recognition. This review will provide inspiration and reference for integrating ML technology into the field of hydrogel flexible sensors. [ABSTRACT FROM AUTHOR]

Perovskite solar cells have seen rapid development over the last decade due to their potential to surpass current market‐leading solar cell technologies. Power conversion efficiency values of perovskite solar cells have reached more than 25 %, making them comparable to their market‐leading silicon‐based counterparts with comparatively few years of development. Whilst large‐scale trials are ongoing, the long‐term stability of perovskite materials remains a significant challenge in their deployment. The first successful perovskite‐based solar cells were lead‐based (Pb‐based). Environmental concerns surrounding Pb‐based perovskites are a significant impediment to their application in industry leading to a substantial increase in research into alternatives that are more environmentally sound. The meta‐analysis study presented in this paper intends to harvest efficiency and synthetic method data from the literature to chart the progress of efficiency over the last decade of BOTH Pb‐ and Sn‐based perovskite solar cells. We then use these data to test the hypothesis: "Did the advancements in the development of earlier Pb‐based perovskite solar cells mean the efficiency of Sn‐based alternatives developed at a faster rate?" The meta‐analysis found that materials engineering, i. e. identifying the suitable materials for perovskite, electron and transport layers and the solution and fabrication process contributed significantly to the rapid annual efficiency growth rates in Pb‐based perovskite solar cells (more than 25 %) from 2011 to 2014. More steady annual efficiency growth rates (2 to 7 %) from 2014 to 2021 are attributed to more advanced compositional engineering, such as optimizing bandgap and addressing stability problems, solution and additive engineering with regard thermal annealing, ageing, doping, improving crystallinity and passivating defects. Ultimately, this report states the challenges Sn‐based perovskite materials face and improvements that will have to be made to become successful on a commercial scale. One of our key findings is the increase in efficiency from 5 % in 2014 to 13 % in 2020 of Sn‐based perovskites making them one of the main contenders to replace Pb‐based perovskites. However, significant challenges remain, including reducing their instability and increasing their efficiencies beyond 20 % to make them competitive against their Pb‐based counterparts. [ABSTRACT FROM AUTHOR]

In this paper, we describe the mechanisms behind the oxidative transformation of vivianite and parasymplesite into formerly not recognized materials that could prove to be novel players in, for example, water splitting or alkali metal intercalation reactions. Based on a sophisticated interpretation of hydrogen‐bonded networks, we were able to identify those phases that have erroneously been classified and to present the crystalline end‐members of the corresponding oxidation chains. [ABSTRACT FROM AUTHOR]

The development of efficient oxygen evolution reaction (OER) catalyst is the key to solve the slow reaction kinetics and is of great significance for the conversion and storage of renewable energy. In this paper, bimetallic/carbon nanosheets electrocatalysts were prepared by high temperature carbonization using Hofmann‐type metal‐organic frameworks (MOFs) as precursors. It is worth noting that in this study, the morphology and structure of the catalyst was successfully adjusted by surfactant, and the Co/Fe‐Dpyz@CNC (1000) catalyst obtained has a large specific surface area (316.3 m2/g) and rich exposed active centers. In addition, the coupling effect of Co and Fe bimetal optimizes the electronic structure of the graphite layer and enhances the conductivity of the catalyst. Co/Fe‐Dpyz@CNC (1000) shows excellent OER performance, the overpotential is 318 mV@10 mA cm−2, and the Tafel slope is very small in 1 M KOH, which is 62.8 mV dec−1. The results show that bimetal/carbon nanosheets are potential catalysts for OER. [ABSTRACT FROM AUTHOR]

A novel fluorescent probe L based on benzimidazole derivative for selective CN− detection was designed and synthesized, and its structure was identified by spectral analysis. In DMSO/H2O (v/v=7 : 3, pH=9) solvent system, the fluorescence intensity for L enhances and the color change from yellow to colorless and purple was immediately observed at 426 nm, but there was no obvious color change when other anions instead of CN− was added to the system. The mechanism on CN− recognition was also studied by 1H NMR, IR, MS analysis and theoretical calculations. The probe L for CN− detection exhibited high sensitivity, and the molar ratio and lowest detection limit was 1 : 1 and 8.2×10−7 mol L−1, respectively. In addition, the probe L could be successfully applied to the detection of CN− in bitter almond, and was also used as a test paper, which indicated that the probe L might conveniently carried out the quick identification and detection of cyanide ion in the environment and food samples through its fluorescent color change under UV lamp. [ABSTRACT FROM AUTHOR]

High Energy Materials (HEMs) is a generic/umbrella term which is used for explosives, propellants & pyrotechnics and form an integral part of almost all weapon systems. A large number of HEMs have been reported in the literature in last few decades. This review paper discusses these HEMs in the light of a new classification of explosives proposed by Agrawal: Thermally stable or Heat‐resistant explosives, High performance (high density & high velocity of detonation) explosives, Melt‐Castable explosives, Insensitive high explosives (IHEs), Energetic binders & plasticizers and Novel energetic materials synthesized with the use of dinitrogen pentoxide (N2O5) technology. This review also critically examines these HEMs from the angles of scalability, processability, safety, reliability and performance in order to ascertain their potential for applications. In the end, problems associated with the use of currently available energetic materials & their likely solutions and areas for further research are also highlighted. [ABSTRACT FROM AUTHOR]

Front Cover: Oxygen out, sulfur in: The alkali metal sulfidotungstates K2[WS4] and novel Na2[WS4] - 4 H2O (Z. Anorg. Sulfidotungstates, thiotungstates, alkali metal, crystal structure, spectroscopy Keywords: sulfidotungstates; thiotungstates; alkali metal; crystal structure; spectroscopy EN sulfidotungstates thiotungstates alkali metal crystal structure spectroscopy 1 1 1 12/15/22 20221213 NES 221213 The cover picture shows an illustration of the paper title, in which we displayed the intention to shift our research interests from oxido- to sulfidotungstates. [Extracted from the article]

I ZAAC i is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co-ordination chemistry. The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super-hard materials, electrical superconductors, or intermetallic compounds. Up-to-date physical methods for the characterization of new chemical compounds and materials are also described. [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

ZAAC is an international scientific journal which publishes original papers on new relevant research results from all areas of inorganic chemistry, solid state chemistry, and co‐ordination chemistry.The contributions reflect the latest findings in these research areas and serve the development of new materials, such as super‐hard materials, electrical superconductors, or intermetallic compounds. Up‐to‐date physical methods for the characterization of new chemical compounds and materials are also described... [Extracted from the article]

Nanoscale phase separation was induced in the K‐doped RuCl3 van der Waals material by annealing, and studied with the goal to find a natural design strategy for the formation of two‐dimensional architectures as an alternative to the costly and time‐consuming experimental artificial growth methods. Phase conversion was traced by means of thermogravimetric analysis combined with mass spectrometry. The local crystal structure of co‐existing K3Ru2Cl9 domains with the sizes of about 100 nm was solved by 3D electron diffraction. [ABSTRACT FROM AUTHOR]

Porous materials‐assisted atmospheric water harvesting (AWH) approaches are attractive for addressing the severe shortage of freshwater resources. Herein, ionothermal polymerization approach was employed to realize four porous organic polymers (FJU‐CTFs) with strong hydration stability and low skeleton density for atmospheric water harvesting. The materials exhibited ultra‐high water vapor adsorption capacity (1108 cm3 g−1), s‐type adsorption isotherms, and rapid filling of water vapor in the pores of the materials under low humidity conditions. It has the characteristics of atmospheric water harvesting from the air at lower humidity (30 %–40 %) and narrow temperature (30–35 °C). A total of 30 times of water adsorption‐desorption cycles showed the excellent working ability and hydrolytic stability of FJU‐CTFs, which provided new solutions for the application of porous materials in AWH and expanded new material types. [ABSTRACT FROM AUTHOR]

The reaction between the heteroleptic metal carbonyl complex [W(CO)4(tmeda)] ((tmeda)=N,N,N′,N′‐Tetramethylethane‐1,2‐diamine) with [Si9]4− silicon Zintl clusters in presence of [2.2.2]crypt ([2.2.2]crypt=4,7,13,16,21,24‐Hexaoxa‐1,10‐diazabicyclo[8.8.8]‐hexacosane) in liquid ammonia yielded the compound [(K,Rb)@([2.2.2]crypt)]2(K,Rb)4[Si9W(CO)4] ⋅ 13.4 NH3. The compound was analyzed by single crystal X‐ray diffraction and crystallizes in the space group P1‾ ${P\bar{1}}$ (a=11.48390(10) Å, b=19.7383(2) Å, c=19.8983(2) Å, α=112.5760(10)°, β=97.4210(10)°, γ=95.3760(10)°, V=4079.01(7) Å3). The compound represents the first group 6 carbonylate‐functionalized silicon Zintl cluster. The central moiety is composed of a tricapped trigonal prismatic nine‐atom silicon species which coordinates with the lone pair of one capping atom to the tungsten tetracarbonylate, forming a pseudo trigonal bipyramidal carbonylate cluster anion [Si9W(CO)4]6−. The chemical bonding in the new cluster entity is analyzed using theoretical calculations and subsequent analysis using QTAIM and NBO. [ABSTRACT FROM AUTHOR]

The syntheses of the new ligands 3‐(pyrazol‐1‐yl)methylpropanoate (L1) and 3‐(2,4‐dimethylpyrazol‐1‐yl)methylpropanoate (L2) and their complexation with palladium(II) have been investigated. In our hands L1 is best prepared by a Michael addition catalyzed by Cs2CO3 and L2 by a catalyst‐ and solvent‐free reaction. Both L1 and L2 react with PdCl2(COD) to produce trans‐PdCl2(L1)2 (3) and trans‐PdCl2(L2)2 (4) respectively. The crystal structures of both new complexes have been determined. An isomerization has been observed when complex 4 is dissolved in CDCl3 or CD3CN. Kinetic data indicate that this is an equilibrium that is first order in both directions. We suggest this may be due to the isomerization of the trans‐ to the cis‐isomer. Their ease of preparation in nearly quantitative yields make the new ligands L1 and L2 potentially useful for further studies. [ABSTRACT FROM AUTHOR]

Reactions of tellurium with metal pentafluorides MF5 (M=As, Sb, Nb, Ta) in liquid SO2 under supercritical conditions at 160 °C yield (Te7)[MF6]2 containing the polymeric Zintl cation (Te72+)n consisting of chair‐shaped Te6 rings connected via single Te atoms. Crystal structure analyses show all four compounds to crystallize isotopically in the (Te7)[AsF6]2 structure type. Monitoring the reactions via Raman spectra reveal that (Te4)[MF6]2 is formed as an intermediate, which reacts with Te finally to (Te7)[MF6]2. Crystal structures of (Te4)[MF6]2 (M=Nb, Ta) were determined. Microwave assisted solvothermal synthesis give analogous results in very short reaction time. All compounds are also accessible via electrochemical oxidation of Te in presence of [MF6]− as electrolyte. (Te7)[AsF6]2 is a semiconductor with σ=10−7 S/cm at 300 K and an energy for the thermally activated electron process of 0.91 eV. Theoretical calculations on the self‐consistent hybrid DFT level confirm that the fundamental band gap is independent from the kind of M. The frontier orbitals are predominantly composed of Te states. Raman bands at 196, 178, 153, and 138 cm−1 are specific for (Te72+)n. Phonon calculations of (Te7)[TaF6]2 confirm three intensive Raman bands at 210, 174 and 163 cm−1. The corresponding normal modes are mainly localized on (Te7)n. [ABSTRACT FROM AUTHOR]

The binary Zintl phase Ba16Sb11 has been synthesized and structurally characterized. Detailed studies via single‐crystal X‐ray diffraction methods indicate that although Ba16Sb11 appears to crystallize in the tetragonal Ca16Sb11 structure type (space group P4‾ ${\overline 4 }$ 21m with a=13.5647(9) Å, c=12.4124(12) Å, Z=2, R1=3.14 %; wR2=4.77 %), there exists an extensive structural disorder. Some Ba16Sb11 crystals were found to be monoclinic and the structure was solved and refined in space group P21 (a=18.3929(12) Å, b=13.5233(8) Å, c=18.3978(12) Å, β=94.6600(10)°; Z=4, R1=5.84 %; wR2=9.58 %). The latter corresponds to a 2‐fold superstructure of the tetragonal one, which provides a disorder‐free structural model. In both descriptions, the disordered tetragonal and the ordered monoclinic superstructure, the basic building units that make up the structure of this Ba‐rich compound are pairs of face‐shared square antiprisms of Ba atoms, which are centered by Sb atoms. The dimerized antiprisms are linked into parallel chains via square prisms of Ba atoms, which are also centered by Sb atoms. The Zintl concept can be applied in a straightforward manner and as result, the structure of Ba32Sb22 (=2×Ba16Sb11) can be rationalized as (Ba2+)32(Sb3−)20[Sb2]4−. The partitioning of the valence electrons is done taking into an account the homoatomic Sb−Sb contacts (d=3.01 Å), which can be clearly distinguished in the lower symmetry space group. Electronic structure calculations of Ba16Sb11 are in good accordance with the Zintl rationalization and predict a semiconductor with a band gap of 0.77 eV. [ABSTRACT FROM AUTHOR]

The B‐site ordered double perovskite Sr2CaOsO6 has been synthesized by a solid‐state reaction under ambient pressure. Sr2CaOsO6 is isostructural to Sr2NaOsO6 and Sr2CaReO6, thus crystallizes in the monoclinic space group P21/n, in contrast to cubic lattice symmetry reported in an earlier publication. The compound remains paramagnetic down to a temperature of 2 K. This finding is of relevance with regard to the high‐temperature ferromagnetism observed in Sr3OsO6 thin films and may find interest in view of possible exotic ground states in frustrated magnetic systems. [ABSTRACT FROM AUTHOR]

So far, homoatomic polybismuthide Zintl anions, which can be used as starting materials for larger binary or ternary, bismuth‐based clusters, have always been isolated from potassium‐based Zintl phases using 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane (crypt‐222) to sequester the K+ counterions. The formation of larger clusters from such anions is still poorly understood, and a change of the sequestering agent might lead to the crystallization of missing links in the cluster formation pathways, which is why – in addition to cost considerations – such variants are being investigated. Herein, we present the synthesis and characterization of the first homoatomic polybismuthide salt with a 1,4,7,10,13,16‐hexaoxacyclooctadecane (18‐crown‐6) complex as counterion, [K(18‐crown‐6)]2Bi2 (1). By means of mass spectrometry, we show that compound 1 behaves, generally, alike [K(crypt‐222)]2Bi2 in reactions with [CpRu(NCMe)3]+, forming the previously reported cluster anion [{CpRu}3Bi6]−. However, crystallization of this cluster can only be achieved in the presence of [PF6]− anions, yielding [{K(18‐crown‐6)}2{PF6}][{CpRu}3Bi6] ⋅ en (2). This shows that [K(18‐crown‐6)]+, if paired up with an additive like [PF6]−, indeed is a (cheaper) alternative for the crystallization of anionic bismuth‐based clusters. [ABSTRACT FROM AUTHOR]

The incorporation of lithium as a filler species in Co1‐2xFexNixSb3 skutterudites was accomplished by intercalation at 60 °C, using n‐BuLi as a reducing agent. Solid state 7Li NMR and ICP‐MS analysis confirm the presence of lithium in the product phases and provide an estimate of the lithium content. The maximum uptake of lithium increases as cobalt is progressively substituted by an equimolar mixture of iron and nickel. Difference Fourier maps, calculated during Rietveld structure refinement using powder neutron diffraction data, locate the lithium cations at the 2a (0,0,0) sites within the cavities of the skutterudite framework. The intercalation of lithium results in reductions in thermal conductivity of up to 47 %, indicative of phonon glass electron crystal (PGEC) type behaviour. Charge transfer from lithium to the framework that accompanies intercalation results in a substantial decrease in electrical resistivity in lithiated phases and a more metal‐like temperature dependence. The increased carrier concentration also decreases the Seebeck coefficient, with the consequence that modest increases in the figure of merit occur, despite the reduced thermal conductivity. [ABSTRACT FROM AUTHOR]

Four compounds with the composition Cd(NCSe)2(3‐ClPy)4 (1), [Cd(NCSe)2(3‐ClPy)2] ⋅ 3‐ClPy (2), Cd(NCSe)2(3‐ClPy)2 (3) and Cd(NCSe)2(3‐ClPy) (4) with 3‐ClPy = 3‐chloropyridine were synthesized. In the structure of 1 discrete complexes are observed, whereas in 2 the Cd cations are linked by pairs of selenocyanato anions into chains and between the chains 3‐chloropyridine solvate molecules are embedded. In compound 3 each two Cd cations are linked by pairs of anionic ligands into dinuclear units, that are further connected into layers by μ‐1,3 single bridging selenocyanate anions. In compound 4, both, octahedrally and tetrahe‐ drally coordinated Cd cations are present, that are linked by μ‐1,3‐ bridging anionic ligands into a three‐.dimensional network. Thermoanalytical investigations prove that compound 1 loses the 3‐chloropyridine ligands stepwise upon heating and transforms into compound 4via compound 3 as an intermediate. Further investigations show that the thiocyanate analogue Cd(NCS)2(3‐ClPy) 5 that is not reported in the literature can also be prepared. Since no single crystals were available, the structure was solved from PXRD data and refined using the Rietveld method, which revealed that this compound is an isomer of 4. In its crystal structure the Cd cations are linked by μ‐1,3(N,S) and μ‐1,3,3(N,S,S)‐bridging anionic ligands into chains that are further connected via Cd2S2 rings into double chains. [ABSTRACT FROM AUTHOR]

Silicon‐based compounds with stereochemical information and convertible functional units are valuable building blocks in synthetic chemistry. Si‐stereogenic aminochlorosilanes are built up by Si−N bond formation between an achiral dichlorosilane and a chiral enantiomerically pure primary amine. Both diastereomers could be isolated as stereochemically pure single‐crystals by fractional crystallization and were analyzed by X‐ray crystallography. Defined intermolecular interaction patterns were identified illustrating the role of N−H⋅⋅⋅π, C−H⋅⋅⋅π, and N−H⋅⋅⋅Cl contacts in the molecular crystalline packing arrangements. Stepwise functionalization of the silicon−chlorine and silicon−amine functions was carried out, demonstrating their potential for use as a chiral synthesis precursors. Via optically pure aminomethoxysilanes, enantiomerically enriched methoxysilanols, chloromethoxysilanes, and methoxysilanethiols were synthesized. The stereospecificity of the transformations was monitored. The (R)‐BINOL‐PSSLi method for determining the enantiomeric purity was found to be the tool of choice for acid‐sensitive silanols and silanethiols. [ABSTRACT FROM AUTHOR]

The structure of the new compound GaGe2Te has been determined using nanofocused synchrotron radiation. The trigonal structure (space group P3‾ ${\overline{3}}$ m1, a=4.0443(3) Å, c=14.923(2) Å, V=211.38(4) Å3; Z=2) consists of Ge bilayers sandwiched by Ga−Te layers. Ge and Ga are tetrahedrally coordinated. The layer packages are separated by a van der Waals gap with a Te−Te distance of 4.1502(7) Å. The structure resembles that of GaGeTe but features an additional Ge atom layer. Despite small scattering contrast of Ga and Ge, precise high‐resolution data enable unequivocal atom assignment as confirmed by R values of different models. DFT calculations suggest only a small extent of charge transfer, which is confirmed by both Bader and Mulliken charges. Thus, bonding within the layer packages is predominantly covalent, especially between Ga and Ge. Formal oxidation states according to GaIIIGe(0)Ge−ITe−II, i. e. assuming rather ionic Ge−Ga bonds, convey a much less realistic situation than GaIIGe2(0)Te−II, which is in line with GaGeTe. [ABSTRACT FROM AUTHOR]

The novel zinc borate Zn2B10O17 was synthesized under high‐pressure/high‐temperature conditions of 8 GPa and 1573 K in a multianvil apparatus. Single‐crystal X‐ray diffraction revealed a unique crystal structure that crystallizes in the orthorhombic non‐centrosymmetric space group Pmc21 (no. 26) with a=769.15(2), b=711.14(2), c=822.14(2) pm, V=0.450(1) nm3 and two formula units (Z=2) per unit cell. The crystal structure is discussed, SHG measurements, and theoretical calculations at HSEsol level of theory were carried out. Herein, we reported about the novel zinc borate Zn2B10O17. It is synthesizable via high‐pressure/high‐temperature solid state reactions and features a unique crystal structure in the non‐centrosymmetric space group Pmc21 (no. 26), which was confirmed by a SHG‐measurement. The structure of Zn2B10O17 consists of an anionic borate framework, that is formed solely by (BO4) units. The zinc atoms are located in channels along the a‐axis and are tetrahedrally and octahedrally coordinated by oxygen atoms. The crystal structure was confirmed by MAPLE, CHARDI, and BL/BS calculations. Furthermore, theoretical calculations at HSEsol level were performed to obtain insight into the band structure properties and the DOS of the zinc borate. Zn2B10O17 is a colourless, ionic compound with a wide band gap of 8.4 eV and is therefore categorized as insulator. [ABSTRACT FROM AUTHOR]

A newly synthesized coordination polymer, [Cd(DMSO)(H2O)]3[Fe(CN)6]2 (CdHCF‐T), based on Cd2+ and Fe(CN)63− ions was prepared in a DMSO/H2O mixed solution and crystalized in the trigonal space group P‐31c. This novel 3D structure presented an interesting single‐crystal to single‐crystal transformation when the coordinated DMSO molecules were replaced by H2O, forming a well‐known Cd Prussian Blue analogue (Cd‐PBA). This occurrence is a rare phenomenon in transition metal hexacyanometallates and may provide a new strategy for obtaining new structures and overcoming the difficulty of growing single crystals of Prussian Blue analogues. Subsequent gas sorption and separation investigations based on the obtained Cd‐PBA were also carried out to evaluate its C2H2/CO2 separation capability. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of four compounds [M(η5‐C5Me5)(N^N)Cl]PF6 [N^N=4,7‐dichloro‐1,10‐phenanthroline with M=Rh, 1, and M=Ir, 2, and N^N=4'‐(4‐chlorophenyl)‐2,2':6',2''‐terpyridine in the κ2N,N'‐coordination mode with M=Rh, 3, and M=Ir, 4] are described. All compounds were characterized by spectroscopic means and their molecular structures in the crystal were confirmed by single‐crystal X‐ray diffraction studies. The cytotoxicity of all compounds was evaluated by MTT assay against the three cancer cell lines HeLa (cervical carcinoma), HT‐29 (colon adenocarcinoma) and MCF‐7 (human breast adenocarcinoma). The complexes 3 and 4 display promising activity with IC50 values of 1 μM. The rhodium(III) complex 1 also shows highly improved cytotoxicity compared to cisplatin against the cancer cell lines HT‐29 and MCF‐7. In contrast to this, the iridium(III) complex 2 is even less active against the HeLa cell line than cisplatin. [ABSTRACT FROM AUTHOR]

We have characterized the layered CuCr(S,Se)2 system for the spin‐polarized electronic band structures and low‐temperature thermoelectric transport properties. The electronic band structure calculations reveal semiconducting behavior for CuCrS2, CuCr(S0.5Se0.5)2 and CuCrSe2 with an indirect bandgap of 0.42, 0.30 and 0.10 eV, respectively. The systematically decreased bandgap with increasing Se content is in line with the experimental observations showing a semiconductor‐to‐metal transition with increasing Se‐substitution level in the CuCr(S1‐xSex)2 system because of an increase in the charge carrier density. The p‐type Seebeck coefficient shows a linear temperature dependence for the samples, like in degenerate semiconductors or metals. The remarkably large Seebeck coefficient even in metallic samples is due to a relatively large effective mass of charge carriers. As the thermal conductivity is intrinsically low owing to the layered crystal structure and is further decreased for the Se‐substituted samples because of the increased phonon scattering from point defects, the thermoelectric characteristics are promising. The highest dimensionless figure‐of‐merit values were seen for the x=0.5 sample, e. g., 0.04 at 400 K. [ABSTRACT FROM AUTHOR]

We present here the syntheses and structural characterizations of inorganic polymeric cluster compounds, Cs[Mn(salen)]3[{Mo6Br6Se2}(CN)6] (1) and (H3O)(TBA)[Mn(salen)]2[{Mo6Br6Se2}(CN)6] (2) (TBA=tetrabutylammonium ((n‐C4H9)4N+)), built‐up from [{Mo6Br6Se2}(CN)6]4− molecular building blocks and Mn(salen)+ complexes (salen = salen = N,N′‐bis(salicylidene)ethylenediamine). The nature of additional counter cations (i. e. Cs+ or TBA+) enables to control the interactions between the [{Mo6Br6Se2}(CN)6]4− building blocks and the Mn(salen)+ groups. Thus, 1 was obtained by slow diffusion of a methanol solution of K2Cs2[{Mo6Br6Se2}(CN)6] cluster compound into a methanol solution of Mn(salen)ClO4. 2 was obtained in a similar way but after the addition of tetrabutylammonium bromide into the solution of Mn(salen)ClO4. 1 is a bimetallic 3D coordination compound (R3‾c ${R\bar{3}c}$) and 2 is a bimetallic 2D compound (P1‾ ${P\bar{1}}$). Structural correlations between 1 and 2 are discussed and compared with relevant examples found in the literature. [ABSTRACT FROM AUTHOR]

The equiatomic ternary BaTX (T=Pd, Pt, Au; X=Mg, Zn, Cd) phases were obtained by reaction of the elements in sealed tantalum ampoules. The compounds were characterized through their X‐ray powder patterns. BaAuMg and BaTCd (T=Pd, Pt, Au) crystallize with the TiNiSi type structure, while the compounds BaTZn (T=Pd, Pt) adopt the ZrBeSi type. The structures of BaAuMg and BaPdZn were refined from single crystal X‐ray diffractometer data: Pnma, a=801.34(5), b=467.71(8), c=924.07(10) pm, wR2=0.0955, 736 F2 values, 20 variables for BaAuMg and P63/mmc, a=449.68(2), c=901.62(4) pm, wR2=0.1172, 145 F2 values, 8 variables for BaPdZn. The structures derive from the aristotype AlB2. The gold and magnesium atoms form puckered Au3Mg3 hexagons with 284–328 pm Au−Mg while the Pd3Zn3 hexagons in BaPdZn are planar (260 pm Pd−Zn). Comparison of all known BaTX phases shows a range of the valence electron count (VEC) from 13 (BaMnGe) to 18 (BaAuP). The BaTX phases crystallize with seven different structure types and there is no obvious correlation with VEC. [ABSTRACT FROM AUTHOR]

Metal pentazolate hydrates have attracted attention because of the unique stabilization mechanisms of cyclo‐N5− anions during crystal stacking. However, coordinated H2O molecules influence the stability of cyclo‐N5− anion‐containing salts, and the structure‐property relationship of high‐valent cobalt pentazolate salts has not been previously reported. Werner‐type cobalt(III) cations that trap cyclo‐N5− anions, a novel class of cyclo‐N5−‐based materials, were prepared and characterized by infrared spectroscopy, elemental analysis, electrospray ionization mass spectrometry, and thermogravimetry with differential scanning calorimetry. The [Co(NH3)5(NO2)]2+ cation was also introduced via metathesis reactions to compare the intermolecular interactions in its intriguing structures. Single‐crystal X‐ray diffraction revealed extensive hydrogen bonding networks in hexaamminecobalt(III) and nitropentamminecobalt(III) cyclo‐N5− salts between cyclo‐N5− anions and NH3 ligands or nitro groups. In addition, [Co(NH3)6(N5)3] (1) and [Co(NH3)5(NO2)](N5)2 (2) exhibited relatively high nitrogen contents of 79.2 % and 67.9 %, respectively, and the impact sensitivities of 1 (IS=5 J) and 2 (IS=4 J) are comparable to that of lead azide. [ABSTRACT FROM AUTHOR]

Photoactive Cu(I) complexes are promising luminescent materials owing to their abundant reserves and marvelous biocompatibility. In this work, we report the synthesis and characterization of two binuclear sulfur‐bridged Cu(I) complexes (POP)2Cu2(μ‐HS/Cl)2 ⋅ 0.92MeOH 1 (POP=(oxybis(2,1‐phenylene))bis(diphenylphosphine)) and (POP)2Cu2(μ‐HS)22, which were prepared by one‐pot facile solvothermal method with copper‐4‐tert‐butylbenzenethiol (CuSC6H4tBu) and POP as precursors. Complex 1 exhibits sky‐blue emission while complex 2 displays blue. Complex 1 was systemically investigated by PXRD, UV‐vis spectrum, IR, TGA and steady‐state spectra. Temperature‐dependent steady‐state emission and decay lifetime indicate that complex 1 is a typical phosphorescent emitter. [ABSTRACT FROM AUTHOR]

A series of lanthanide metal‐organic frameworks (MOFs) have been assembled with a series of functionalized [1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylic acid ligands. The relationship between the ligand properties and the corresponding MOF properties has been studied. The structures of the MOFs depend on the solvent‐ligand and ligand‐ligand interactions, as well as the size of the non‐coordinating functional groups of the ligands. The differences in thermal stability among the ligands are inherited and amplified by corresponding lanthanide MOFs. The ligands bearing methyl, ether, and aldehyde functional groups are capable of sensitizing the emission from the lanthanide centers, whereas the ligand with α,β‐unsaturated ketone functional groups are non‐emissive due to the mismatch of the ligand and metal energy levels. [ABSTRACT FROM AUTHOR]

Herein, we report about the preparation of several new 2,6‐diisopropylphenyl (Dipp) substituted (halido‐) bismuthanes, namely, Dipp3Bi (1) and compounds of the form DippBiX2 (X=Cl, Br, I; 2–4). The compounds 2–4 show a variety of structural motifs in their solid state structures. Reactivity of 2 towards the nucleophiles LiNMe2 and MeLi was examined, where mostly scrambling reactions with a preference for two Dipp substituents at bismuth were observed. Therefore, the compounds Dipp2BiNMe2 (5) and Dipp2BiMe (6) are the main products of these reactions. Moreover, new interpnictogen compounds with Bi−N, ‐P, and ‐Sb single bonds were prepared. Compound 5 was successfully used as precursor for the preparation of Dipp2BiNHtBu (7) and Dipp2BiSbMes2 (8), one of very few isolated compounds with a Bi‐Sb single bond. Moreover, bismuthanyl phosphanes bearing functional groups (Dipp2BiPtBu(SiMe3) (9), Dipp2BiPHtBu (10)) have been prepared. Compound 10 is the first isolated secondary phosphane with a bismuthanyl substituent. All isolated compounds were analyzed via IR and NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X ray diffraction. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of six new organometallic half‐sandwich iridium(III) compounds containing modified 4,4'‐substituted 2,2'‐bipyridines as the bidentate co‐ligands were described. Thus the compounds [Ir(η5‐C5Me5)(N^N)Cl]PF6 [N^N: 4,4'‐bpy‐Ph, 1; 4,4'‐bpy‐Me, 2; 4,4'‐bpy‐nonyl, 3; 4,4'‐bpy‐CH2OH, 4; 4,4'‐bpy‐Cl, 5; 4,4'‐bpy‐NH2, 6 were obtained by bridge‐splitting reactions from the precursor [{Ir(η5‐C5Me5)(μ‐Cl)Cl}2] with the corresponding bidentate bipyridines. The X‐ray single‐crystal structures of compounds 1, 2, 4 and 6 in the solid state were determined. To evaluate the cytotoxic properties of all six compounds, colorimetric assays (MTT assay) against two cancer cell lines, MCF‐7 and HT‐29, were performed. Most promising results were achieved for compounds 1 and 3 with nonpolar phenyl or nonyl group attached to the bipyridine ligand, while the substitution with less lipophilic groups led to the inactivation of the compound. The most remarkable biological activity showed compound 3 with an IC50 value in the low macromolecular range and >40‐fold enhanced toxicity compared to cisplatin against both cell lines. [ABSTRACT FROM AUTHOR]

Three protocols that involve the cleavage of the Au−P bond in Au‐substituted phosphines (AuPhos) have been demonstrated, namely i) direct demetallation with a strong anionic base; ii) protonation followed by demetallation with a neutral base; iii) oxidation‐triggered metal migration. Specifically, direct demetallation of (CAAC)AuPPh2 (1 a) (CAAC=cyclic (alkyl)(amino)carbene) with KP(TMS)2 or LiC(N2)TMS yields (CAAC)AuPTMS2 (2) or (CAAC)AuC(N2)TMS (3), respectively. Treatment of (NHC)AuPPh2 (1 b) (NHC=N‐heterocyclic carbene) with HOTf followed by the corresponding neutral phosphine gives scarce examples of aurophosphonium salts [(NHC)AuPHAd2][OTf] (5) and [((NHC)Au)2PPh2][OTf] (6). Oxidation of 1 a or 1 b with Se affords LAuSeP(Se)Ph2 (L=CAAC, 7 a; NHC, 7 b). [ABSTRACT FROM AUTHOR]

Molecular β‐diketiminato (BDI) calcium hydride and n‐hexyl derivatives are shown to display contrasting reactivities toward bis(pinacolato)diboron (B2pin2). Whereas the dimeric constitution of the calcium hydride is retained during formation of an unusual diborane(6) dianion, the initially dimeric organocalcium reagent is converted to a calcium diboranate monomer, [(BDI)Ca{pinB‐Bpin(n‐hex)}]. Attempts to effect heterolysis of the B−B bond of this latter species in a manner reminiscent of a previously reported magnesium system were unsuccessful and resulted in either dismutation to the homoleptic β‐diketiminate, [(BDI)2Ca], or, in the case of organic nitriles, the generation of N‐donor adduct derivatives, [(BDI)Ca(NCR){pinB‐Bpin(n‐hex)}] (R=t‐Bu, i‐Pr, o‐tol). This latter reactivity again contrasts with the previously reported behaviour of an analogous magnesium diboranate, observations that are rationalised by density functional theory (DFT) calculations to be effectively a consequence of the larger radius and lower resultant steric congestion, of the third‐row group 2 cation. [ABSTRACT FROM AUTHOR]

Alkaline‐earth metalation of dimesitylphosphane oxide Mes2P(O)H (1) in ethereal solvents with dialkylmagnesium and alkylmagnesium bromide as well as the homoleptic bis(trimethylsilyl)amides of calcium, strontium, and barium yields [(L)MgR(μ‐OPMes2)]2 (L/R=thf/Et (2‐Et), Et2O/Br (2‐Br)), [(thf)3Ca(hmds)(OPMes2)] (3‐hmds), [(thf)3Mg(OPMes2)2] (2‐thf) and [(thf)4Ae(OPMes2)2] (Ae=Ca (3‐thf), Sr (4‐thf), and Ba (5‐thf)), depending on the applied stoichiometry. Exchange of thf ligands in 3‐thf by oligodentate ethers allows isolation of [(thf)2(dme)Ca(OPMes2)2] (3‐dme), [(thf)2(diglyme)Ca(OPMes2)2] (3‐diglyme) and [(thf)(triglyme)Ca(OPMes2)2] (3‐triglyme). Contrary to this finding, oligodentate amines are unable to substitute ligated thf ligands in 3‐thf. In ethereal solutions, the heteroleptic complexes 2‐Et, 2‐Br and 3‐hmds show Schlenk‐type equilibria, interconverting these compounds into their homoleptic counterparts. [ABSTRACT FROM AUTHOR]