Inorganics

The unexpected tetranuclear [Cu₄(DPPT)₂Cl₆] complex was obtained by self-assembly of CuCl₂.2H₂O and (E)-2,4-di(piperidin-1-yl)-6-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)-1,3,5-triazine, (HDPPT) in ethanol. In this tetranuclear [Cu₄(DPPT)₂Cl₆] complex, the organic ligand acts as mononegative chelate bridging two crystallographically independent Cu(II) sites. The DPPT⁻ anion acts as a bidentate ligand with respect to Cu(1), while it is a tridentate for Cu(2). The Cu(1)N₂Cl₃ and Cu(2)N₃Cl spheres have square pyramidal and square planar coordination geometries with some distortion, respectively. Two of the chloride ions coordinating the Cu(1) are bridging between two crystallographically related Cu(1) sites connecting two [Cu₂(DPPT)Cl₃] units together, leading to the tetranuclear formula [Cu₄(DPPT)₂Cl₆]. The packing of the [Cu₄(DPPT)₂Cl₆] complex is dominated by C-H…Cl contacts, leading to one-dimensional hydrogen-bond polymeric structure. According to Hirshfeld surface analysis of molecular packing, the non-covalent interactions H…H, Cl…H, Cl…C, C…H, and N…H are the most significant. Their percentages are 52.8, 19.0, 3.2, 7.7, and 9.7%, respectively. Antimicrobial assessment showed good antifungal activity of the Cu(II) complex against A. fumigatus and C. albicans compared to Ketoconazole as positive control. Moreover, the [Cu₄(DPPT)₂Cl₆] complex has higher activity against Gram-positive bacteria than Gentamycin as positive control. The opposite was observed when testing the tetranuclear [Cu₄(DPPT)₂Cl₆] complex against the Gram-negative bacteria. Full article

In an attempt to fill in the empty Zn position in the “Periodic Table” of 1-methylbenzotriazole (Mebta), reactions between Zn(II) sources and this ligand were carried out. The detailed synthetic studies provided access to complexes [ZnX₂(Mebta)₂] (X = Cl, 1; X = Br, 3; X = I, 4), (MebtaH)₂[ZnCl₄] (2), tet-[Zn(NO₃)₂(Mebta)₂] (5), oct-[Zn(NO₃)₂(Mebta)₂] (6), and [Zn(Mebta)₄](Y)₂ [Y = ClO₄, 7; Y = PF₆, 8]. Solid-state thermal decomposition of 2 leads to 1 in quantitative yield. The structures of 3, 4, 5, 6, and 7 were determined by single-crystal crystallography. The structures of the remaining complexes were proposed based on spectroscopic evidence. In all compounds, Mebta behaves as monodentate ligand using the nitrogen of the position 3 as donor. Complexes 1–4, 7, and 8 are tetrahedral. Complexes 5 and 6 are isostoichiometric and their preparation in pure forms depends on the reaction conditions; in the former the Zn^II atom has a tetrahedral geometry, whereas in the latter the metal ion is octahedral. This case of rare isomerism arises from the monodentate (in 5) vs. bidentate (in 6) coordination of the nitrato groups. Extensive π–π stacking interactions and non-classical H bonds build interesting 3D architectures in the structurally characterized complexes. The compounds were characterized by IR, far-IR, and Raman spectroscopies in the solid state, and the data were interpreted in terms of the structures (known or proposed) of the complexes and the coordination modes of the organic and inorganic ligands involved. The solid-state structures of the complexes are not retained in solution, as proven by NMR (¹H, ¹³C[¹H]) spectroscopy and molar conductivity data. The thermal decomposition study of 1 and 3 leads to stable intermediates with 1:1 stoichiometry, i.e., ZnX₂(Mebta). Based on far-IR spectra, polymeric tetrahedral structures are possible with simultaneous presence of terminal and bridging X⁻ groups. Liquid-phase ab initio (MP2) and gas-phase DFT calculations, performed on Mebta and the nitrato complexes, respectively, shed light on the tendency of Mebta for N3-coordination, and the existence and relative stabilities of 5 and 6. Full article

Aluminum oxide production from aluminum filings, which are a byproduct of several industrial machining processes and cannot be recycled to attain bulk aluminum (Al), is vital due to its wide use in scientific research and industry. The goal of this paper is to produce ultrafine and down-to-the-nanoscale alumina powder (Al₂O₃), starting from a waste Al filings. The microstructure and composition of the starting Al used were investigated using scanning electron microscopy (SEM), which was equipped with an attached energy dispersive spectrometer (EDS) unit. The results of this investigation confirmed that the starting Al was mainly Al–Mg alloy. Al₂O₃ was produced using two routes: The first involved the burning of aluminum hydroxide Al(OH)₃ that was precipitated from aluminum chloride solution (AlCl₃) resulting from dissolving the Al filings in 2M HCl. The second route involved direct precipitation as a reaction product of aluminum chloride with sodium carbonate solution. The Al₂O₃ produced using both routes, as well as the intermediate product Al(OH)₃, were studied by SEM. The results demonstrate that the nanoscale range size was reached after milling of the produced Al₂O₃. Following thorough washing with distilled water, the EDS and the XRD techniques confirmed the formation of Al₂O₃, with no residual salt detected. The EDS results showed that the ratios of Al and O in the produced Al₂O₃ were about 96% of the ideal compound ratios. The XRD analysis also revealed the amorphous structure of the standard and the produced Al(OH)₃, whereas the phases of the produced Al₂O₃ were either crystalline or amorphous. In our study, the Al₂O₃ percentage yield was about 77%, and this value obviously depends on the percentage of Al dross in the original Al filings. Overall, this research provides a novel contribution to the production of alumina powder in the nano-range starting from an aluminum filings byproduct, thereby reducing the dependence on known sources of aluminum. Full article

This research work highlights the tribomechanical investigations of using a low loading fraction of two ceramics combinations, Alumina (Al₂O₃) and Silicon Carbide (SiC) as reinforcement for Low-density Polyethylene (LDPE) matrix. The hybrid additives with different weight percentages (0.1 + 0.1, 0.25 + 0.25 and 0.5 + 0.5 wt%) were mixed with LDPE matrix and the degree of homogeneity was controlled using double-screw extruder prior to fabricating the composite samples via the injection molding machine. The nanoparticles fillers were characterized by field emission scanning electron microscope (FESEM), EDX and particle size analyzer to check its morphology, composition and size distribution. Thermogravimetric analyzer (TGA) and melting flow index (MFI) were performed for the fabricated nanocomposites samples. The mechanical properties of the nanocomposite were evaluated by performing tensile test, bending test and Shore-D hardness test, while the tribological performance was investigated using a ball on desk apparatus under different applied loads and sliding times. Moreover, in order to confirm the load-carrying capability of the composite, contact stresses was measured via finite element model using ANSYS software. The results show that the incorporation of low fraction hybrid ceramic nanoparticles can contributed positively in the tribological and mechanical properties. Based on the experimental results, the maximum improvement in the tensile strength was 5.38%, and 8.15% for hardness LDPE with 0.5 Al₂O₃ and 0.5 SiC, while the lowest coefficient of friction was noticed under normal load of 10 N, which was approximately 12.5% for the same composition. The novel approach of incorporating low fraction hybrid ceramic nanoparticles as reinforcement for LDPE matrix is investigated, highlighting their positive contributions to the tribological and mechanical properties of the resulting nanocomposites. Full article

Pyrazino-phenanthroline ligands are commonly used with transition metals as DNA intercalation agents. Herein, we report the characterization of two commonly utilized pyrazino-phenanthroline ligands, dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq) and (benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), by single-crystal X-ray diffraction. Additionally, the characterization of [Ir(ppy)₂(dppn)][PF₆], where Hppy = 2-phenylpyridine, by single-crystal X-ray diffraction is described. Both the dpq and dppn ligands crystallize as chloroform solvates where the chloroform molecule occupies the equivalent binding pocket of a metal in metal complexes of these ligands. These pyrazino-phenanthrolines are largely planar, with the dppn ligand displaying a slight twist. When the dppn ligand is coordinated to iridium(III), the dppn ligand on the resulting complex displays a significant degree of bending along the longitudinal direction of the ligand. This iridium (III) complex crystallizes as a CH₂Cl₂ and Et₂O solvate and due to the volatility of these solvents these crystals are only stable for a few seconds outside of the mother liquor. The structures of the free ligands and the [Ir(ppy)₂(dppn)][PF₆] complex all display extensive π stacking interactions. Full article

Copper/sulfur co-doped titanium dioxide-carbon nanofibers (Cu,S-codoped TiO₂ NPs, decorated-CNFs) catalysts were synthesized using the electrospinning process to produce composite nanofibers (NFs). These composite NFs were utilized for the hydrolysis of sodium borohydride (SBH) to generate hydrogen gas (H₂), taking advantage of their catalytic properties. The experimental results demonstrated that using 100 mg of composite NFs yielded the highest catalytic activity for H₂ production, generating 79 mL of H₂ gas within 6 min at 25 °C and 1000 revolutions per minute (rpm) using 1 mmol of SBH. As the catalyst dosage was reduced from 100 mg to 75, 50, and 25 mg, the reaction time increased by 9, 13, and 18 min, respectively. Kinetic studies revealed that the reaction rate followed a first-order reaction, indicating a direct proportionality between the rate of reaction and the catalyst amount. Additionally, it was observed that the concentration of SBH had no influence on the reaction rate, suggesting a zero-order reaction. Increasing the reaction temperature resulted in a reduced reaction time. The activation energy was determined to be 26.16 kJ mol⁻¹. The composite NFs maintained their superior performance over five iterations. These findings suggest that composite nanofibers have the potential to serve as a cost-effective alternative to expensive catalysts in hydrogen production. Full article

Reported are the synthesis and structural characterization of a series of quaternary lithium-alkaline earth metal alumo-silicides and alumo-germanides with the base formula A₂LiAlTt₂ (A = Ca, Sr, Ba; Tt = Si, Ge). To synthesize each compound, a mixture of the elements with the desired stoichiometric ratio was loaded into a niobium tube, arc welded shut, enclosed in a silica tube under vacuum, and heated in a tube furnace. Each sample was analyzed by powder and single-crystal X-ray diffraction, and the crystal structure of each compound was confirmed and refined from single-crystal X-ray diffraction data. The structures, despite the identical chemical formulae, are different, largely dependent on the nature of the alkaline earth metal. The differing cation determines the structure type—the calcium compounds are part of the TiNiSi family with the Pnma space group, the strontium compounds are isostructural with Na₂LiAlP₂ with the Cmce space group, and the barium compounds crystallize with the PbFCl structure type in the P4/nmm space group. The anion (silicon or germanium) only impacts the size of the unit cell, with the silicides having smaller unit cell volumes than the germanides. Full article

The [Ag(3ADMT)(NO₃)]_n complex was synthesized by the self-assembly of 3-amino-5,6-dimethyl-1,2,4-triazine (3ADMT) and AgNO₃. Its molecular structure was analyzed utilizing FTIR spectra, elemental analysis, and single crystal X-ray diffraction (SC-XRD). There is one crystallographically independent Ag atom, which is tetra-coordinated by two nitrogen atoms from two 3ADMT and two oxygen atoms from two nitrate anions where all ligand groups are acting as connectors between the Ag1 sites. The geometry around the Ag(I) center is a distorted tetrahedron with a AgN₂O₂ coordination sphere augmented by strong argentophilic interactions between Ag atoms, which assist the aggregation of the complex units in a wavy-like and coplanar pattern to form a one-dimensional polymeric chain. The O...H (37.2%) and N...H (18.8%) intermolecular interactions contributed significantly to the molecular packing based on Hirshfeld surface analysis. The [Ag(3ADMT)(NO₃)]_n complex demonstrates promising cytotoxicity against lung (IC₅₀ = 2.96 ± 0.31 μg/mL) and breast (IC₅₀ = 1.97 ± 0.18 μg/mL) carcinoma. This remarkable cytotoxicity exceeds those of 3ADMT, AgNO₃, and the anticancer medication cis-platin towards the tested cancer cell lines. In addition, the complex has a wide-spectrum antimicrobial action where the high antibacterial potency of the [Ag(3ADMT)(NO₃)]_n complex against P. vulgaris (MIC = 6.1 µg/mL) and B. subtilis (MIC = 17.2 µg/mL) could be comparable to the commonly used drug Gentamycin (MIC = 4.8 µg/mL). These results confirm that the components of the [Ag(3ADMT)(NO₃)]_n complex work together synergistically, forming a powerful multifunctional agent that could be exploited as an effective antimicrobial and anticancer agent. Full article

The reactivity of the open-shell Gd@C_2v-C₈₂ with different charge states towards benzyl bromide was investigated. [Gd@C_2v-C₈₂]³⁻ exhibited enhanced activity relative to Gd@C_2v-C₈₂ and [Gd@C_2v-C₈₂]⁻. The structural characterizations, including MALDI-TOF MS, UV-vis-NIR, and single crystal X-ray diffraction, indicate the formation of isomeric benzyl monoadducts of Gd@C_2v-C₈₂. All three monoadducts contain 1:1 mirror-symmetric enantiomers. Additionally, the addition of the benzyl group and its specific position result in distinct electrochemical behavior of the products compared to the parent Gd@C_2v-C₈₂. Theoretical studies demonstrate that only [Gd@C_2v-C₈₂]³⁻ has a HOMO energy level that matches well with the LUMO energy level of the PhCH₂ radical, providing a rationalization for the observed significantly different reactivity. Full article

Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design for clusters and synthetic strategies for modifying the cluster cores. The present study investigates the chemistry of a class of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers of varying lengths (ⁿPDI₂, n = 2, 3). A series of dicopper complexes bound by the ⁿPDI₂ ligands are described and found to exhibit improved solubility over their parent analogs due to the incorporation of 4-^tBu groups on the pyridyl units and the use of triflate counterions. The ensuing synthetic study investigated methods for introducing various bridging ligands (µ-X; X = F, Cl, Br, N₃, NO₂, OSiMe₃, OH, OTf) between the two copper centers within the macrocycle-supported complexes. Traditional anion metathesis routes were unsuccessful, but the abstraction of bridging halides resulted in “open-core” complexes suitable for capturing various anions. The geometric flexibility of the ⁿPDI₂ macrocycles was reflected in the various solid-state geometries, Cu–Cu distances, and relative Cu coordination spheres on variation in the identity of the captured anion. Full article

This article focuses on the galvanic replacement synthesis of Ti-Ni and Zr-Ni metal systems with a “core-shell” structure, which are potential precursors for intermetallics. The authors defined effective synthesis parameters and formation features of polymetallic systems characterized by granulometric, phase, and elemental composition. X-ray fluorescence and X-ray phase analysis methods showed that the deposition of nickel on dispersed titanium and zirconium leads to the production of test samples with phase composition representing a mechanical mixture of Ni and Ti, and Ni and Zr. The method of X-ray fluorescence analysis showed that the presence of hydrofluoric acid with a 0.5-1.5 M concentration results in the formation of fixed quantitative ratios of elements in the precipitate, which allows the quantitative composition of dispersed systems “titanium-nickel” and “zirconium-nickel” to be regulated within a relatively wide range. Scanning electron microscopy proved that all synthesized systems are characterized by a highly porous structure that follows the titanium and zirconium particle surface contour and the presence of spherical nanoscale subunits on the formed particle surface. Full article

Functionalization of endohedral metallofullerenes (EMFs) plays an important role in exploring the reactivity of EMFs and stabilizing missing EMFs, thus conferring tunable properties and turning EMFs into applicable materials. In this review, we present exhaustive progress on the functionalization of EMFs since 2019. Classic functionalization reactions include Prato reactions, Bingel–Hirsch reactions, radical addition reactions, carbene addition reactions, and so on are summarized. And new complicated multi-component reactions and other creative reactions are presented as well. We also discuss the structural features of derivatives of EMFs and the corresponding reaction mechanisms to understand the reactivity and regioselectivity of EMFs. In the end, we make conclusions and put forward an outlook on the prospect of the functionalization of EMFs. Full article

The thermal reduction of the copper(II) complexes [Cu^II(N₂H₄)₃][B₁₀H₁₀]·nH₂O (I·nH₂O) and [Cu^II(NH₃)₄][B₁₀H₁₀]·nH₂O (II·nH₂O) has been studied in an argon atmosphere at 900 °C. It has been found that the annealing of both compounds results in a Cu@BN boron-containing copper composite. It has been shown that this process leads to the formation of a boron nitride matrix doped with cubic copper(0) nanoparticles due to the copper(II)→copper(I)→copper(0) thermal reduction. The phase composition of annealing products I⁹⁰⁰ and II⁹⁰⁰ has been determined based on powder X-ray diffraction, IR spectroscopy and thermal analysis data. The morphology, average particle size and composition of the composite have been determined by TEM and high-resolution TEM + EDS. The average particle size has been found to be about 81 nm and 52 nm for samples I⁹⁰⁰ and II⁹⁰⁰, respectively. Comparison of the results obtained using physicochemical studies has shown the identity of the composition of the products of annealing I⁹⁰⁰ and II⁹⁰⁰. The electrical properties of a coating based on an I⁹⁰⁰ sample modified with Cu⁰→Cu₂O in situ during deposition on a chip at 300 °C in air have been studied. As a result, with increasing temperature, an increase in the electrical conductivity characteristic of semiconductors has been observed. Full article

Background: The system of self-consistent models is an attempt to develop a tool to assess the predictive potential of various approaches by considering a group of random distributions of available data into training and validation sets. Considering many different splits is more informative than considering a single model. Methods: Models studied here build up for solubility of fullerenes C60 and C70 in different organic solvents using so-called quasi-SMILES, which contain traditional simplified molecular input-line entry systems (SMILES) incorporated with codes that reflect the presence of C60 and C70. In addition, the fragments of local symmetry (FLS) in quasi-SMILES are applied to improve the solubility’s predictive potential (expressed via mole fraction at 298’K) models. Results: Several versions of the Monte Carlo procedure are studied. The use of the fragments of local symmetry along with a special vector of the ideality of correlation improves the predictive potential of the models. The average value of the determination coefficient on the validation sets is equal to 0.9255 ± 0.0163. Conclusions: The comparison of different manners of the Monte Carlo optimization of the correlation weights has shown that the best predictive potential was observed for models where both fragments of local symmetry and the vector of the ideality of correlation were applied. Full article

In this study, we investigated the preparation conditions of polystyrene (PS)@TiO₂ core–shell particles and their photocatalytic activity during the decomposition of methylene blue (MB). TiO₂ shells were formed on the surfaces of PS particles using the sol–gel method. Homogeneous PS@TiO₂ core–shell particles were obtained using an aqueous NH₃ solution as the promoter of the sol–gel reaction and stirred at room temperature. This investigation revealed that the temperature and amount of the sol–gel reaction promoter influenced the morphology of the PS@TiO₂ core–shell particles. The TiO₂ shell thickness of the PS@TiO₂ core–shell particles was approximately 5 nm, as observed using transmission electron microscopy. Additionally, Ti elements were detected on the surfaces of the PS@TiO₂ core–shell particles using energy-dispersive X-ray spectroscopy analysis. The PS@TiO₂ core–shell particles were used in MB decomposition to evaluate their photocatalytic activities. For comparison, we utilized commercial P25 and TiO₂ particles prepared using the sol–gel method. The results showed that the PS@TiO₂ core–shell particles exhibited higher activity than that of the compared samples. Full article

In this study, 2D Co-B nanosheet-decorated 1D TiO₂ nanofibers (2D Co-B NS-decorated 1D TiO₂ NFs) are synthesized via electrospinning and an in situ chemical reduction technique. The as-prepared catalyst showed excellent catalytic performance in H₂ generation from sodium borohydride (SBH). When compared to naked Co-B nanoparticles, the catalytic activity of the 2D Co-B NS-decorated 1D TiO₂ NFs catalyst for the hydrolysis of SBH is significantly enhanced, as demonstrated by the high hydrogen generation rate (HGR) of 6020 mL min⁻¹ g⁻¹ at 25 °C. The activation energy of hydrolysis was measured to be 30.87 kJ mol⁻¹, which agreed with the reported values. The catalyst also showed good stability. Moreover, the effects of SBH, catalyst concentration, and temperature on the catalytic performance of 2D Co-B NS-decorated 1D TiO₂ NFs were studied to gain a comprehensive understanding of the dehydrogenation mechanism of SBH. Based on these findings, we conclude that 2D Co-B NS-decorated 1D TiO₂ NFs are effective catalytic materials for the dehydrogenation of SBH. Full article

In this study, the Mg²⁺-doped anatase TiO₂ phase was synthesized via the solvothermal method by changing the ratio of deionized water and absolute ethanol V_water/V_ethanol). This enhances the bleaching efficiency under visible light. The crystal structure, morphology, and photocatalytic properties of Mg-doped TiO₂ were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, N₂ adsorption-desorption, UV-Vis spectroscopy analysis, etc. Results showed that the photocatalytic activity of the Mg²⁺-doped TiO₂ sample was effectively improved, and the morphology, specific surface area, and porosity of TiO₂ could be controlled by V_water/V_ethanol. Compared with the Mg-undoped TiO₂ sample, Mg-doped TiO₂ samples have higher photocatalytic properties due to pure anatase phase formation. The Mg-doped TiO₂ sample was synthesized at V_water/V_ethanol of 12.5:2.5, which has the highest bleaching rate of 99.5% for the rhodamine B dye during 80 min under visible light. Adding Mg²⁺-doped TiO₂ into the phase-separated glaze is an essential factor for enhancing the self-cleaning capability. The glaze samples fired at 1180 °C achieved a water contact angle of 5.623° at room temperature and had high stain resistance (the blot floats as a whole after meeting the water). Full article