Inorganic

Two deep ultraviolet (DUV) hydroxylated-alkali-metal borates, NaRbB10 O14 (OH)4 (I) and Na3 CsB10 O16 (OH)2 (II), have been successfully synthesized by a high-temperature solution and solvothermal method. Both of them feature [B5 O m (OH) n ] units, which form chains for (I) and bilayers with nine-membered boron rings for (II). It is worth noting that both compounds exhibit very wide theoretical band gaps of 7.33 and 6.55 eV for (I) and (II), respectively, which denotes that they should have desirable DUV transmittance ability...

A novel class of (P^N^C) pincer ligands capable of stabilizing elusive gold(III) species is reported here. Straightforward access to (P^N^C)gold(III) hydroxo, formate, and hydride complexes has been streamlined by first incorporating a cycloauration step devoid of toxic metals or harsh conditions. The resulting gold complexes exhibit remarkable stability in solution as well as in the solid state under ambient conditions, which enabled their characterization by X-ray diffraction analyses. Interestingly, the influence of the ligand allowed the preparation of gold(III)-hydrides using mild hydride donors such as H-Bpin, which contrasts with sensitive super hydrides or strong acids and cryogenic conditions employed in previous protocols...

Cuprous thiocyanate (CuSCN) emerges as a prime candidate among inorganic hole-transport materials, particularly suitable for the fabrication of perovskite solar cells. Nonetheless, there is an Ohmic contact degradation between the perovskite and CuSCN layers. This is induced by polar solvents and undesired purities, which reduce device efficiency and operational stability. In this work, we introduce amidinothiourea (ASU) as an intermediate layer between perovskites and CuSCN to overcome the above obstacles...

Careful manipulation of the plutonium oxidation states is essential in the study and utilization of its rich redox chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. To this end, we have developed an experimentally evaluated multiscale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1...

Since the 1980s, the paddlewheel effect has been suggested as a mechanism to boost lithium-ion diffusion in inorganic materials via the rotation of rotor-like anion groups. However, it remains unclear whether the paddlewheel effect, defined as large-angle anion group rotations assisting Li hopping, indeed exists; furthermore, the physical mechanism by which the anion-group dynamics affect lithium-ion diffusion has not yet been established. In this work, we differentiate various types of rotational motions of anion groups and develop quaternion-based algorithms to detect, quantify, and relate them to lithium-ion motion in ab initio molecular dynamics simulations...

Nitridophosphates and nitridogermanates attract high interest in current research due to their structural versatility. Herein, the elastic properties of GeP2 N4 were investigated by single-crystal X-ray diffraction (XRD) upon compression to 44.4(1) GPa in a diamond anvil cell. Its isothermal bulk modulus was determined to be 82(6) GPa. At 44.4(1) GPa, laser heating resulted in the formation of multiple crystalline phases, one of which was identified as unprecedented germanium nitridophosphate GePN3 . Its structure was elucidated from single-crystal XRD data ( C 2/ c (no...

High-power LED lighting is a crucial challenge due to the notorious thermal quenching (TQ) effect of traditional phosphors at high operating currents, which would result in poor device performance and hamper practical optoelectronic application. Herein, we demonstrate ligand engineering of a cubane- versus staircase-like [Cu4 I4 ] conformer as a node in coordination polymers, which remarkably suppresses the TQ effect of cluster-based photoluminescence. For complex 1 (the formula [Cu4 I4 (bbimb)2 ] n ) with the cubane-like [Cu4 I4 ] conformer as a node, the metallophilicity interaction enables ultrabright triplet emission with a photoluminescence quantum yield over 82%, and the phonon-assisted detrapping process of excitons effectively suppresses the TQ effect in the wide temperature range...

Uptake of thiosulfate ions as an inorganic sulfur source from the environment is important for bacterial sulfur assimilation. Recently, a selective thiosulfate uptake pathway involving a membrane protein YeeE (TsuA) in Escherichia coli was characterized. YeeE-like proteins are conserved in some bacteria, archaea, and eukaryotes. However, the precise function of YeeE, along with its potential partner protein in the thiosulfate ion uptake pathway, remained unclear. Here, we assessed selective thiosulfate transport via Spirochaeta thermophila YeeE in vitro and characterized E...

The use of elephant ivory as a commodity is a factor in declining elephant populations. Despite recent worldwide elephant ivory trade bans, mammoth ivory trade remains unregulated. This complicates law enforcement efforts, as distinguishing between ivory from extant and extinct species requires costly, destructive and time consuming methods. Elephant and mammoth ivory mainly consists of dentine, a mineralized connective tissue that contains an organic collagenous component and an inorganic component of calcium phosphate minerals, similar in structure to hydroxyapatite crystals...

Vanadium oxides exhibit promising characteristics for electrochemical energy storage, owing to their capability to switch between different oxidation states, in combination with the incorporation of alkali metals. Here, we report on a systematic investigation of the mechanochemical reduction of V2 O5 with NaH. In contrast to conventional high-temperature synthesis methods, the mechanochemical reaction occurs already after a few minutes. We observed a mixture of different (sodium) vanadium oxides with vanadium oxidation states ranging from +III to +V...

Isocyanates play an essential role in modern manufacturing processes, especially in polyurethane production. There are numerous synthesis strategies for isocyanates both under industrial and laboratory conditions, which do not prevent searching for alternative highly efficient synthetic protocols. Here, we report a detailed theoretical investigation of the mechanism of sulfur dioxide-catalyzed rearrangement of phenylnitrile oxide into phenyl isocyanate, which was first reported in 1977. The DLPNO-CCSD(T) method and up-to-date DFT protocols were used to perform a highly accurate quantum-chemical study of the rearrangement mechanism...

The mitochondrial phosphate carrier is critical for adenosine triphosphate synthesis by serving as the primary means for mitochondrial phosphate import across the inner membrane. Variants in the SLC25A3 gene coding mitochondrial phosphate carrier lead to failure in inorganic phosphate transport across mitochondria. The critical dependence on mitochondria as an energy source is especially evident in tissues with high-energy demands such as the heart, muscle; defects in the mitochondrial energy production machinery underlie a wide range of primary mitochondrial disorders that present with cardiac and muscle diseases...

In recent years, all-inorganic perovskite materials have become an ideal choice for new thin film solar cells due to their excellent photophysical properties and have become a research hotspot. Studying the ultrafast dynamics of photo-generated carriers is of great significance for further improving the performance of such devices. In this work, we focus on the transient dynamic process of CsPbBr3/TiO2 composite systems with different Mn2+ doping contents using femtosecond transient absorption spectroscopy technology...

Boron compounds have attracted the attention of chemists because of their unique catalytic properties and potential wider material applications. Although group 13 metal compounds, which are based on the bis-(benzoxazol-2-yl)-methane system (Box, ({NCOC6 H4 }2 CH2 )), have been reported in the last several years, boron containing Box compounds were still missing. Now we report their successful syntheses and spectroscopic characterisation in this work. The borane compound [({NCOC6 H3 }2 CH)BH2 ] (1) and haloboranes [({NCOC6 H3 }2 CH)BF2 ] (2), [({NCOC6 H3 }2 CH)BCl2 ] (3) and [({NCOC6 H3 }2 CH)BBr2 ] (4) were characterised in the solid state by single crystal X-ray diffraction and in solution by NMR techniques...

We report two dinuclear rhenium(V) oxo complexes 1 and 2 types, [ReV (O)(Cl)3 (L2- )ReV (O)(Cl)3 ][NBu4 ]2 (1, L2- = dianionic 2,5-dihydroxy 1,4-benzoquinone (DBQ2- )) and (2, L2- = dianionic chloranilic acid (CA2-) ligands), as a homogeneous electrocatalyst for water oxidation reactions in the acetonitrile-water mixture. The evolution of dioxygen gas at the anode was confirmed by a GC-TCD study. In controlled potential electrolysis (CPE), oxidation at 1.30 V ( vs. Ag/AgCl) at neutral pH, 1 and 2 afforded 1+ [ReVI (O)(Cl)3 (DBQ˙3- )ReVI (O)(Cl)3 ]- and 2+ [ReVI (O)(Cl)3 (CA˙3- )ReVI (O)(Cl)3 ]- ions, respectively, via the redox induced electron transfer (RIET) process...

Graphene, renowned for its exceptional physicochemical attributes, has emerged as a favored substrate for integrating a wide array of inorganic and organic materials in scientific endeavors and innovations. Electrochemical graphene-based nanocomposite sensors have been developed by incorporating diverse nanoparticles into graphene, effectively immobilized onto electrodes through various techniques. These graphene-based nanocomposite sensors have effectively detected and quantified various electroactive species in samples...

Mild aqueous electrolytes containing multivalent metal salts are currently scrutinized for the development of ecosustainable energy-related devices. However, the role of soluble multivalent metal ions in the electrochemical reactivity of transition metal oxides is a matter of debate, especially when they are performed in protic aqueous electrolytes. Here, we have compared, by means of (spectro)electrochemistry, the reversible electrochromic reduction of transparent nanostructured γ-WO3 thin films in mild aqueous electrolytes of various chemical composition and pH...

The borane-functionalized (BR2 ) bis(3,5-dimethylpyrazolyl)methane ( L H ) ligands 1a (BR2 : 9-borabicyclo[3.3.1]nonane or 9-BBN), 1b (BR2 : BCy2 ), and 1c (BR2 : B(C6 F5 )2 ) were synthesized by the allylation-hydroboration of L H . Metalation of 1a,b with ZnCl2 yielded the heteroscorpionate dichloride complexes [(1a,b)ZnCl 2 ] 3a,b . The reaction of 1a with ZnEt2 led to the formation of the zwitterionic complex [Et(1a)ZnEt(THF)] 5 . The reaction of complex 3a with two equivalents of KHBEt3 under a carbon dioxide (CO2 ) atmosphere gave rise to the formation of the dimeric bis(formate) complex [(1a)Zn(OCHO) 2 ] 2 8 , in which its borane moieties intermolecularly stabilize the formate ligands of opposite metal centers...

A series of ligands based upon a 1,3-diimino-isoindoline framework have been synthesized and investigated as pincer-type (N∧ N∧ N) chelates for Pt(II). The synthetic route allows different combinations of heterocyclic moieties (including pyridyl, thiazole, and isoquinoline) to yield new unsymmetrical ligands. Pt( L 1-6 )Cl complexes were obtained and characterized using a range of spectroscopic and analytical techniques: 1 H and 13 C NMR, IR, UV-vis and luminescence spectroscopies, elemental analyses, high-resolution mass spectrometry, electrochemistry, and one example via X-ray crystallography which showed a distorted square planar environment at Pt(II)...

Organic selenium (Se) accounts for up to 10-80% of total Se in soils, and l-selenomethionine (SeMet) is a typical organic Se species. However, the migration of SeMet in soils remains elusive. This study investigated the solid-liquid distribution, adsorption, desorption by phosphate, and self-oxidization of SeMet in solution under the influence of ferrihydrite, goethite, and hematite through batch experiments. Iron oxides could adsorb a much larger amount of SeMet than inorganic Se. At the initial Se element concentrations of 0-200 mg/L, the solid/liquid partition coefficient of SeMet was constant, which was 0...