Inorganics

The reaction of ammoniacal AgNO₃ solution (or aq. solution of [Ag(NH₃)₂]NO₃) with aq. NaClO₄ resulted in [Ag(NH₃)₂]ClO₄ (compound 1). Detailed spectroscopic (correlation analysis, IR, Raman, and UV) analyses were performed on [Ag(NH₃)₂]ClO₄. The temperature and enthalpy of phase change for compound 1 were determined to be 225.7 K and 103.04 kJ/mol, respectively. We found the thermal decomposition of [Ag(NH₃)₂]ClO₄ involves a solid-phase quasi-intramolecular redox reaction between the perchlorate anion and ammonia ligand, resulting in lower valence chlorine oxyacid (chlorite, chlorate) components. We did not detect thermal ammonia loss during the formation of AgClO₄. However, a redox reaction between the ammonia and perchlorate ion resulted in intermediates containing chlorate/chlorite, which disproportionated (either in the solid phase or in aqueous solutions after the dissolution of these decomposition intermediates in water) into AgCl and silver perchlorate. We propose that the solid phase AgCl-AgClO₄ mixture eutectically melts, and the resulting AgClO₄ decomposes in this melt into AgCl and O₂. Thus, the final product of decomposition is AgCl, N₂, and H₂O. The intermediate (chlorite, chlorate) phases were identified by IR, XPS, and titrimetric methods. Full article

As the world evolves, so does the energy demand. The storage of hydrogen using metal hydrides shows great promise due to the ability to store and deliver energy on demand while achieving higher volumetric density and safer storage conditions compared with traditional storage options such as compressed gas or liquid hydrogen. Research is typically performed on lab-sized samples and tanks and shows great potential for large scale applications. However, the effects of scale-up on the metal hydride’s performance are relatively less investigated. Studies performed so far on both materials, and hydride-based storage tanks show that the scale-up can significantly impact the system’s capacity, kinetics, and sorption properties. The findings presented in this review suggest areas of further investigation in order to implement metal hydrides in real scale applications. Full article

Magnesium-based hydrides are considered as promising candidates for solid-state hydrogen storage and thermal energy storage, due to their high hydrogen capacity, reversibility, and elemental abundance of Mg. To improve the sluggish kinetics of MgH₂, catalytic doping using Ti-based catalysts is regarded as an effective approach to enhance Mg-based materials. In the past decades, Ti-based additives, as one of the important groups of catalysts, have received intensive endeavors towards the understanding of the fundamental principle of catalysis for the Mg-H₂ reaction. In this review, we start with the introduction of fundamental features of magnesium hydride and then summarize the recent advances of Ti-based additive doped MgH₂ materials. The roles of Ti-based catalysts in various categories of elemental metals, hydrides, oxides, halides, and intermetallic compounds were overviewed. Particularly, the kinetic mechanisms are discussed in detail. Moreover, the remaining challenges and future perspectives of Mg-based hydrides are discussed. Full article

A new mixed alkali metal–aluminum borohydride LiAl(BH₄)₂Cl₂ has been prepared via mechanochemical synthesis from the 2LiBH₄–AlCl₃ mixture. Structural characterization, performed using a combination of X-ray powder diffraction and solid-state NMR methods, indicates that the LiAl(BH₄)₂Cl₂ phase adopts a unique 3D framework and crystallizes in an orthorhombic structure with the space group C222₁, a = 11.6709(6) Å, b = 8.4718(4) Å, c = 7.5114(3) Å. The material shows excellent dehydrogenation characteristics, where hydrogen evolution starts at Tons = 70 °C, releasing approximately 2 wt.% of nearly pure (99.8 vol.%) hydrogen and a very small amount (~0.2 vol.%) of diborane. When compared to halide-free mixed alkali metal–aluminum borohydrides, the presence of Al‒Cl bonding in the LiAl(BH₄)₂Cl₂ structure likely prevents the formation of Al(BH₄)₃ upon decomposition, thus suppressing the formation of diborane. Full article

Mono- and binuclear arene–ruthenium(II) complexes with imidazole-containing ligands were prepared by the reaction of the ligands (L¹ = bis(imidazole-1-yl)methane; ImH = 1H-Imidazole; BImH = 1H-Benzimidazole) with [(p-cym)Ru(µ-Cl)₂]₂ dimers. When bis(imidazole-1-yl)methane reacted with [(p-cym)Ru(µ-Cl)₂]₂ in methanol, a binuclear complex of the type [Ru₂(L¹)₂(p-cym)₂Cl₂]Cl₂ (2) with cyclic structure was synthesized, whereas by using acetonitrile as a solvent under the same reaction conditions, an unexpected C–N bond cleavage was observed, and a complex of formula [Ru(ImH)₂(p-cym)Cl]Cl (1) with coordinated imidazole molecules was obtained. Another type of arene–ruthenium complex [Ru(BImH)(p-cym)Cl₂] (3) was obtained by the reaction of benzimidazole and [(p-cym)Ru(µ-Cl)₂]₂. All compounds were characterized by spectral (FT-IR, NMR ¹H, ¹³C) and single-crystal X-ray diffraction methods; their catalytic activity in transfer hydrogenation and the cytotoxicity against MCF-7 and HepG2 cells were evaluated. Full article

Metal–Organic Frameworks (MOFs) and Coordination Polymers (CPs) are at the forefront of contemporary coordination chemistry research, as witnessed by the impressive (and ever-growing) number of publications appearing in the literature on this topic in the last 20 years (Figure 1), reaching almost 4000 papers in 2020 [...] Full article

The development of supramolecular systems showing aurophilic interactions in solution is gaining much attention in the last years. This is due to the intriguing photophysical properties of gold(I) complexes, which usually confer to these supramolecular assemblies interesting luminescent properties, as well as the possibility of morphological modulation, through fine tuning of inter- and intramolecular aurophilic interactions, in synergy with the formation of other supramolecular contacts. In this work, an overview of the advances made in this area since 2015 is presented. A large variety of systems showing different spectroscopical and structural topologies has been reported. Moreover, these supramolecular assemblies have proven to be useful in a wide range of applications. Full article

Information resulting from a comprehensive investigation into the intrinsic strengths of hydrated divalent magnesium clusters is useful for elucidating the role of aqueous solvents on the Mg²⁺ ion, which can be related to those in bulk aqueous solution. However, the intrinsic Mg–O and intermolecular hydrogen bond interactions of hydrated magnesium ion clusters have yet to be quantitatively measured. In this work, we investigated a set of 17 hydrated divalent magnesium clusters by means of local vibrational mode force constants calculated at the $\omega$B97X-D/6-311++G(d,p) level of theory, where the nature of the ion–solvent and solvent–solvent interactions were interpreted from topological electron density analysis and natural population analysis. We found the intrinsic strength of inner shell Mg–O interactions for [Mg(H₂O)_n]²⁺ (n = 1–6) clusters to relate to the electron density at the bond critical point in Mg–O bonds. From the application of a secondary hydration shell to [Mg(H₂O)_n]²⁺ (n = 5–6) clusters, stronger Mg–O interactions were observed to correspond to larger instances of charge transfer between the lp(O) orbitals of the inner hydration shell and the unfilled valence shell of Mg. As the charge transfer between water molecules of the first and second solvent shell increased, so did the strength of their intermolecular hydrogen bonds (HBs). Cumulative local vibrational mode force constants of explicitly solvated Mg²⁺, having an outer hydration shell, reveal a CN of 5, rather than a CN of 6, to yield slightly more stable configurations in some instances. However, the cumulative local mode stretching force constants of implicitly solvated Mg²⁺ show the six-coordinated cluster to be the most stable. These results show that such intrinsic bond strength measures for Mg–O and HBs offer an effective way for determining the coordination number of hydrated magnesium ion clusters. Full article

Separate reactions of [Th{N(CH₂CH₂NSiMe₂Bu^t)₂(CH₂CH₂NSi(Me)(Bu^t)(μ-CH₂)]₂ (1) with [Re(η⁵-C₅H₅)₂(H)] (2) or [Ru(η⁵-C₅H₅)(H)(CO)₂] (3) produced, by alkane elimination, [Th(Tren^DMBS)Re(η⁵-C₅H₅)₂] (ThRe, Tren^DMBS = {N(CH₂CH₂NSiMe₂Bu^t)₃}^3-), and [Th(Tren^DMBS)Ru(η⁵-C₅H₅)(CO)₂] (ThRu), which were isolated in crystalline yields of 71% and 62%, respectively. Complex ThRe is the first example of a molecular Th-Re bond to be structurally characterised, and ThRu is only the second example of a structurally authenticated Th-Ru bond. By comparison to isostructural U-analogues, quantum chemical calculations, which are validated by IR and Raman spectroscopic data, suggest that the Th-Re and Th-Ru bonds reported here are more ionic than the corresponding U-Re and U-Ru bonds. Full article

The anharmonic phonon behavior in zirconium hydrides and deuterides, including ϵ-ZrH₂, γ-ZrH, and γ-ZrD, has been investigated from aspects of inelastic neutron scattering (INS) and lattice dynamics calculations within the framework of density functional theory (DFT). The harmonic model failed to reproduce the spectral features observed in the experimental data, indicating the existence of anharmonicity in those materials and the necessity of further explanations. Here, we present a detailed study on the anharmonicity in zirconium hydrides/deuterides by exploring the 2D potential energy surface of hydrogen/deuterium atoms and solving the corresponding 2D single-particle Schrödinger equation to obtain the eigenfrequencies, which are then convoluted with the instrument resolution. The convoluted INS spectra qualitatively describe the anharmonic peaks in the experimental INS spectra and demonstrate that the anharmonicity originates from the deviations of hydrogen potentials from quadratic behavior in certain directions; the effects are apparent for the higher-order excited vibrational states, but small for the ground and first excited states. Full article

Synthesis, isolation, and structural characterization of unique metal rich diamagnetic cobaltaborane clusters are reported. They were obtained from reactions of monoborane as well as modified borohydride reagents with cobalt sources. For example, the reaction of [Cp*CoCl]₂ with [LiBH₄·THF] and subsequent photolysis with excess [BH₃·THF] (THF = tetrahydrofuran) at room temperature afforded the 11-vertex tricobaltaborane nido-[(Cp*Co)₃B₈H₁₀] (1, Cp* = η⁵-C₅Me₅). The reaction of Li[BH₂S₃] with the dicobaltaoctaborane(12) [(Cp*Co)₂B₆H₁₀] yielded the 10-vertex nido-2,4-[(Cp*Co)₂B₈H₁₂] cluster (2), extending the library of dicobaltadecaborane(14) analogues. Although cluster 1 adopts a classical 11-vertex-nido-geometry with one cobalt center and four boron atoms forming the open pentagonal face, it disobeys the Polyhedral Skeletal Electron Pair Theory (PSEPT). Compound 2 adopts a perfectly symmetrical 10-vertex-nido framework with a plane of symmetry bisecting the basal boron plane resulting in two {CoB₃} units bridged at the base by two boron atoms and possesses the expected electron count. Both compounds were characterized in solution by multinuclear NMR and IR spectroscopies and by mass spectrometry. Single-crystal X-ray diffraction analyses confirmed the structures of the compounds. Additionally, density functional theory (DFT) calculations were performed in order to study and interpret the nature of bonding and electronic structures of these complexes. Full article

Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into functional MOF construction for diverse applications. Here, we will focus on how organometallic chemistry is applied in MOF design and modifications from linker-centric and metal-cluster-centric perspectives, respectively. Through structural design, MOFs can function as a tailorable platform for traditional organometallic transformations, including reaction of alkenes, cross-coupling reactions, and C–H activations. Besides, an overview will be made on other application categories of organometallic MOFs, such as gas adsorption, magnetism, quantum computing, and therapeutics. Full article

Platinum-based anticancer drugs are most likely the most successful group of bioinorganic compounds. Their apparent disadvantages have led to the development of anticancer compounds of other noble metals, resulting in several ruthenium-based drugs which have entered clinical trials on oncological patients. Besides ruthenium, numerous rhodium complexes have been recently reported as highly potent antiproliferative agents against various human cancer cells, making them potential alternatives to Pt- and Ru-based metallodrugs. In this review, half-sandwich Rh(III) complexes are overviewed. Many representatives show higher in vitro potency than and different mechanisms of action (MoA) from the conventional anticancer metallodrugs (cisplatin in most cases) or clinically studied Ru drug candidates. Furthermore, some of the reviewed Rh(III) arenyl complexes are also anticancer in vivo. Pioneer anticancer organorhodium compounds as well as the recent advances in the field are discussed properly, and adequate attention is paid to their anticancer activity, solution behaviour and various processes connected with their MoA. In summary, this work summarizes the types of compounds and the most important biological results obtained in the field of anticancer half-sandwich Rh complexes. Full article

The relevance of multidimensional and porous crystalline materials to nuclear waste remediation and storage applications has motivated exploratory research focused on materials discovery of compounds, such as actinide mixed-oxoanion phases, which exhibit rich structural chemistry. The novel phase K_1.8Na_1.2[(UO₂)BSi₄O₁₂] has been synthesized using hydrothermal methods, representing the first example of a uranyl borosilicate. The three-dimensional structure crystallizes in the orthorhombic space group Cmce with lattice parameters a = 15.5471(19) Å, b = 14.3403(17) Å, c = 11.7315(15) Å, and V = 2615.5(6) ų, and is composed of UO₆ octahedra linked by [BSi₄O₁₂]⁵⁻ chains to form a [(UO₂)BSi₄O₁₂]³⁻ framework. The synthesis method, structure, results of Raman, IR, and X-ray absorption spectroscopy, and thermal stability are discussed. Full article

A mononuclear ruthenium complex, [Ru^II(L)(bpy)₂](PF₆), with a naphthoquinone-annelated imidazole ligand HL (2-(pyridin-2-yl)-1H-naphtho[2,3-d]imidazole-4,9-dione) was synthesized and structurally characterized. Electrochemical study reveals that the Ru complex shows four reversible redox waves at +0.98 V, −1.13 V, −1.53 V, and −1.71 V versus SCE in acetonitrile, which are assigned to Ru(II)/Ru(III), L⁻/L^•2−, and two bpy/bpy^•− redox couples, respectively. The redox potential of Ru(II)/Ru(III) was positively shifted upon the addition of trifluoromethanesulfonic acid due to protonation of the L⁻ moiety, leading to stabilization of the Ru 4d orbital. In UV-vis absorption measurements for the Ru complex in acetonitrile, a metal-to-ligand charge transfer (MLCT) band was observed at 476 nm, which was shifted to 450 nm by protonation, which might be due to a decrease in the electron delocalization and stabilization of the π orbitals in L⁻. The blue shift of the MLCT band by protonation was associated with a shift of an emission band from 774 nm to 620 nm, which could be caused by the decreased electronic delocalization in the MLCT excited state. These electrochemical and spectroscopic changes were reversible for the protonation/deprotonation stimuli. Full article

This work pertains to Cr³⁺ and Nd³⁺ co-activated Ca₂MgWO₆ phosphors synthesized by high temperature solid-state method using oxides and carbonates as raw materials. All luminescent samples according to Ca₂MgWO₆:Cr³⁺,Nd³⁺ include Cr³⁺ for the absorption of UV and visible radiation (230–800 nm) prior to energy transfer to Nd³⁺. As a result of the energy transfer between Cr³⁺ and Nd³⁺, we observe line emission originating from Nd³⁺ in the near infrared range additionally to the broad band near infrared emission from Cr³⁺ assigned to the spin-allowed ⁴T₂ → ⁴A₂ transition. The energy transfer from Cr³⁺ to Nd³⁺ is discussed via the variations of the lifetime data of Cr³⁺ and Nd³⁺. The strong absorption of Cr³⁺ in the ultraviolet range and the efficient energy transfer from Cr³⁺ to Nd³⁺ indicate that the herein presented material type can serve as a radiation converter for near infrared region light emitting diodes (NIR-LEDs) comprising an UV-A emitting (Al,Ga)N chip. Full article

Development of catalysts for the selective hydrolysis of proteins is challenging, yet important for many applications in biotechnology and proteomics. The hydrolysis of hydrophobic proteins is particularly challenging, as due to their poor solubility, the use of surfactants is often required. In this study, the proteolytic potential of catalyst systems based on the Zr(IV)-substituted Keggin polyoxometalate (Et₂NH₂)₁₀[Zr(PW₁₁O₃₉)₂] (Zr-K 1:2) and three different surfactants (ionic SDS (sodium dodecyl sulfate); zwitterionic Zw3-12 (n-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate); and CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate)), which differ in structure and polarity, has been investigated. Hydrolysis of ovalbumin (OVA) was examined in the presence of Zr-K 1:2 and surfactants by sodium dodecyl sulfate poly(acrylamide) gel electrophoresis (SDS-PAGE), which showed the appearance of new polypeptide fragments at lower molecular weight, indicating that selective hydrolysis of OVA took place for all three catalyst systems. The same fragmentation pattern was observed, showing that the selectivity was not affected by surfactants. However, the surfactants influenced the performance of the catalyst. Hence, the interactions of OVA with surfactants and Zr-K 1:2 were investigated using different techniques such as tryptophan fluorescence, Circular Dichroism, and Dynamic Light Scattering. The speciation of the catalyst in surfactant solutions was also followed by ³¹P Nuclear Magnetic Resonance spectroscopy providing insight into its stability under reaction conditions. Full article

Multicompound TiO₂/SiO₂ nanoparticles with a diameter of 50–70 nm were generated using a liquid flame spray (LFS) nanoparticle deposition in a single flame. Here, we study the photocatalytic activity of deposited multicompound nanoparticles in gas-phase via oxidation of acetylene into carbon dioxide that gives new insight about the multicompound nanoparticle morphology. A small addition of SiO₂ content of 0.5%, 1.0% and 3.0% significantly suppressed the photocatalytic activity by 33%, 44% and 70%, respectively, whereas 5.0% SiO₂ addition completely removed the activity. This may be due to a formation of a thin passivating SiO₂ layer on top of the of the TiO₂ nanostructures during the LFS nanoparticle deposition. Surface wetting results support this hypothesis with a significant increase in water contact angle as the SiO₂ content is increased. Full article

Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H₂L) of general formulae [Zn(L)(H₂O)]_n (1) and [Cd₂(HL)₄]_n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds. Full article