A layered MOF Co-Tdp-Bpy was designed based on the Hard–Soft-Acid–Base (HSAB) theory, and exhibited excellent activity and stability in the OER.

Unconventional luminescence caused by hindered intra- and intermolecular mobility of molecules is of great research interest in science and technology. However, the lack of data on the effect of the structure of such compounds on the process of aggregation-induced emission and the underdevelopment of existing synthetic approaches make these studies difficult. We have developed new non-classical luminophores based on amidophosphonate and amidophosphate containing polysilsesquioxanes obtained by a simple two-stage synthetic route: monomers were obtained by nucleophilic substitution reactions at the P(V) atom, and the corresponding polymers were obtained by hydrolytic polymerization. Luminescent properties of both monomers and polymers were described, and it was shown that luminescence by cluster aggregation is also characteristic of low-molecular luminophores.

The barrier to rotation of the unsubstituted cyclopentadienyl (Cp) ring in the crystal of rac-N, N-dimethyl-1-ferrocenylethylammonium (Ugi’s amine) bromide was investigated using variable‑temperature single‑crystal X‑ray diffraction (SC XRD) and Mössbauer spectroscopy. The gas‑phase rotational barrier for the Ugi’s amine cation, previously determined by density functional theory (DFT) calculations for the analogous benzoate salt, is 4.2 kJ/mol, indicating a negligible intramolecular contribution. In the present crystalline hydrobromide salt, the experimental barrier derived from TLS analysis of anisotropic displacement parameters over the temperature range 150–300 K is significantly higher, varying from 7.5 to 8.1 kJ/mol. This increase provides direct evidence for the dominant role of intermolecular interactions – specifically C–H···Br and C–H···π contacts – in restricting Cp‑ring rotation in the solid state. The obtained barrier values are consistent with Case I behavior (molecules in general positions). Complementary Mössbauer spectroscopy yields a Debye temperature of 147 K, indicating a rigid crystal environment that correlates with the elevated rotational barrier. The results confirm our previously established correlation between the barrier height and crystallographic symmetry, and demonstrate the effectiveness of combining SC XRD with TLS analysis and Mössbauer spectroscopy for studying molecular dynamics in crystalline ferrocenes.

Cycloaddition reaction of 1-alkyl-1,2-diphospholes with alkynes is regarded as a new way for the synthesis of pentasubstituted phosphinines. The [4 + 2] cycloaddition of 1-ethyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-diene to bis(2-thienyl)acetylene gives new 2,3-(2-thienyl)-4,5,6-triaryl-1-phosphinines along with formation of ethylphosphinidene [:P–Alk].

Inorganic nanomaterials based on rare-earth elements hold great promise for biomedical applications, particularly in bioimaging. For such applications, it is essential for nanoparticles to form stable colloidal dispersions in water and biological fluids. Therefore, the development of efficient hydrophilization strategies becomes a key challenge. One effective approach involves a one-step ligand exchange with 3,4-dihydroxybenzoic acid (3,4-DHB), followed by stabilization with polyethyleneimine (PEI) and was successfully applied here to hydrophobic (oleate-stabilized) core-shell nanoparticles (NaYF4:Yb/Er@NaGdF4:Ce/Tb-C/S). The resulting water-dispersible C/S/3,4-DHB/PEI nanoparticles form stable aqueous colloidal solutions while preserving their luminescent properties, through both upconversion and downshifting process, as well as their structural integrity. In this study we demonstrate that C/S/3,4-DHB/PEI nanoparticles can be used as efficient bimodal agents for optical and magnetic resonance imaging (MRI). Confocal near-infrared fluorescence microscopy reveals their ability to visualize the intricate morphology of a living grape snail's nervous system with a spatial resolution of-1 mu rn. Furthermore, they enable highly accurate temperature measurements within the physiological range (280-350 K), with a temperature sensitivity of 0.85 % K-1 at 300 K. C/S/3,4-DHB/PEI nanoparticles also show promise as contrast agents for Tl-weighted MRI (1.5 T), demonstrating a transverse relaxivity of 3.2 mM-1s1, comparable to that of commercial MRI contrast agents such as GdDTPA (3.9 mM-ls-1). These findings highlight the potential of C/S/3,4-DHB/PEI nanoparticles as versatile tools for biomedical applications, combining optical imaging, temperature sensing, and MRI capabilities.

An eco-friendly and selective synthesis based on the thiol-ene reaction under mild conditions was used to obtain a series of alkylthio-substituted carboxylic acids (TAA-n) and their salts (TSA-n) (n = 6, 8, 10, 16). The structure of the amphiphiles synthesized were confirmed using 1H, 13C NMR, and FTIR spectroscopy, and elemental analysis. The critical aggregation concentration (CAC) was determined using a combination of physicochemical techniques, i.e., tensiometry, conductometry, dynamic light scattering, and transmission electron microscopy. It was established that the aggregation ability increases with the elongation of the alkyl tail, as well as with the transition from salts to acids. The presence of a thioether group in the amphiphile structure has a notable influence on the hydrophilic-lipophilic balance of the molecule, promoting the enhancement of intermolecular interactions and, consequently, leading to a reduction in the CAC compared to the aggregation threshold of conventional sulfur-free carboxylate surfactants. At concentrations above the CAC, the formation of large aggregates is observed. Their binary systems with nonionic surfactant Tween 80 showed a synergistic effect, testifying the formation of mixed aggregates. This was evidenced by lower CAC values compared to individual amphiphiles and by increased Orange OT solubilization detected using spectrophotometry. The surfactants exhibited pronounced wetting ability, as evidenced by a decrease in the water contact angle on a hydrophobic Parafilm (R) surface from 114 degrees to 45 degrees (TAA-8), accompanied by a threefold increase in the spreading area. TSA-16 further demonstrated the ability to generate stable foam with a lifetime exceeding 30 min, indicating its potential as an effective foaming agent.

This review explores the advancements and potential of electrochemical methods in the synthesis of silicon-containing polymers (mainly polysilanes and silicones), a critical area of organosilicon chemistry. Traditional widely used silicon-containing polymers production methods face significant challenges due to the reliance on organochlorine compounds, which are hazardous to handle and pose environmental risks. Electrochemical approaches offer a promising alternative, providing greater control over reaction conditions, minimizing the formation of by-products, and enabling the use of more environmentally friendly precursors. This review highlights the various electrochemical techniques applied in the synthesis of polysilanes and silicones, including both oxidative and reductive processes. It also discusses the potential for these methods to address existing limitations in silicon-containing polymers production, such as high energy consumption and complex purification steps. Furthermore, the review highlights the direct electrochemical functionalization of silicon dioxide SiO2 as a particularly underexplored area, presenting a significant opportunity for future research. The integration of electrochemical methods in silicon-containing polymers synthesis not only aligns with the goals of green chemistry but also opens up new avenues for industrial applications, promising more sustainable and efficient production pathways.

In this study, a new method for producing a composite material composed of epoxy resin and 0.03wt.% modified graphene oxide (MLGO) was developed and tested, where the MLGO was concentrated near one surface of the composite using a magnetic field. This feature reduced the wear rate of that surface by 87% compared to pure epoxy resin and by 17% compared to the uniform distribution of MLGO in the epoxy matrix. Concentrating MLGO near the surface proved to be the most effective strategy for improving wear resistance, as it also prevented crack formation. Moreover, the MLGO nanofiller not only enhances mechanical properties and wear resistance but also imparts magnetic sensitivity and luminescence, making it a valuable component for advanced materials.

A method for synthesizing N,N-diethyl-P-methylphosphonamidic chloride via the reaction of methylphosphonic dichloride with diethylamine is presented. The structures of methylphosphonic dichloride and N,N-diethyl-Pmethylphosphonamidic chloride were confirmed using single-crystal X-ray diffraction, as well as nuclear magnetic resonance and infrared spectroscopies. The formation of the 3D crystal structure is facilitated to the multiple nonclassical hydrogen bonds formed between the oxygen atom of the P=O group and the hydrogen atoms of the P-CH3 methyl group.

Organophosphorus compounds are important in synthetic organic chemistry and pharmaceutical applications due to their diverse biological activities. In this study, we synthesized three novel glycidyl esters of phosphorus acids 1-3 via the condensation of chlorophosphine oxides or phosphorus oxychloride with glycidol in the presence of a base, obtaining products with high purity and moderate to excellent yields. Their cytotoxic potential was evaluated using the MTT assay on human fibroblasts (HSF), prostate cancer (PC-3), and breast cancer (MCF7) cell lines, revealing moderate preferential cytotoxicity toward cancer cells, particularly in the case of MCF7. Additionally, linear sweep voltammetry (LSV) studies on human serum albumin (HSA) were conducted to investigate their alkylating properties. The electrochemical results suggest that these compounds effectively modify albumin, highlighting their potential as reactive anticancer agents. These findings provide important insights into the synthesis, cytotoxic activity, and biochemical reactivity of glycidyl esters of phosphorus acids, underscoring their potential as lead structures for further development in anticancer drug discovery and pharmaceutical research.

Synthesis and detailed morphological, structural, and photophysical analysis were conducted on core@shell NaYF4:Yb/Er@NaGdF4:Ce/Tb nanoparticles (C/S NPs). It was found that the NaGdF4:Ce/Tb shell significantly reduces defects in the NaYF4:Yb/Er core, enhancing the emission resolution of Er3+ ions. These C/S NPs exhibit dual luminescence functionality: upconversion with a quantum yield of 0.19 %, driven by energy transfer between Yb3+ and Er3+ ions, and downshifting luminescence with a remarkable quantum yield of 96 %, attributed to the energy transfer between Ce3+ and Tb3+ ions. Polymer nanocomposites, polystyrene-C/S (PS-C/S), and polyvinyl acetate-C/S (PVA-C/S) were synthesized by co-dissolving the polymers and nanoparticles in chloroform, followed by the removal of chloroform. Thin films based on the PS-C/S composite exhibited upconversion luminescence, enabling spatial temperature measurements with a lateral resolution of 10 mu m and an accuracy of 1.6 K on a non-uniformly heated sample. The PVA-C/S composite exhibited dual-mode luminescence (upconversion and downshifting), which was employed to create fluorescent images activated by either NIR or UV irradiation. Additionally, these images demonstrated high stability against alcohols, acetone, and alkaline aqueous solutions, offering new anti-counterfeiting measures.

Our study compares the structural, photophysical, and electrochemical characteristics of 3,4,5- triphenyl-1-neomenthyl-1,2-diphosphole (1) and 3,4,5-triphenyl-1-mesityl-1,2-diphosphole (2). Experimental and optimized geometries of 1-R-1,2-diphospholes are close to each other and imply a significant delocalization within the 1,2-diphosphole ring for both molecules. Both compounds exhibit a green solid-state emission, whereas the DCM solutions are non-emissive. The preliminary electrochemical oxidation followed by electrochemical reduction leads to the anion-radical paramagnetic form, which is stable for 1-aryl-1,2-diphosphole, but unstable for 1-alkyl-1,2-diphosphole. The radical nature of 2(center dot-) was confirmed by in situ EPR-spectroelectrochemistry along with DFT calculations and in situ UV/Vis-spectroelectrochemistry.

The reaction of [NiBr(aryl)(bpy)] organonickel complexes with sodium 1,2-diphospholide leads to unknown 1-aryl-1,2-diphospholes by aryl group transfer.

The synthesis of tetraaryl-substituted 1-monophospholes and 1-monophosphaferrocenes, bearing 4-bromophenyl and 2-thienyl substituents at the PCα carbon atoms are described. It was shown that the reaction of n-octyl chloride with a mixture of sodium 1,2,3-tri- and 1-monophospholides results in the exclusive formation of new luminescent 1-n-octyl-1-monophospholes. All novel compounds have been fully characterized by NMR spectroscopy and mass-spectrometry, their optical and electrochemical behaviors have been elucidated. Phosphaferrocene-based compounds exhibit higher oxidation stability and higher HOMO-LUMO separation compared to the corresponding 1-monophosphole units.

A new representative of 1,2-diphosphaferrocenes containing p-fluorophenyl substituents on the 1,2-diphosphacyclopentadienyl ring was synthesized. Its structure was confirmed by multinuclear NMR, IR, and Mössbauer spectroscopy, and its electrochemical properties were studied.

The purpose of this review is to summarize recent advances in inorganic and organometallic polymers as electrode materials for supercapacitors. The review discusses the advantages and disadvantages of various electrode materials, including activated metal oxides and hydroxides, coordination polymers, and their composites. Inorganic and coordination polymers have attracted high interests as electrode materials for electrochemical capacitors, because of their electrical conductivity, high surface area, low cost and chemical stability. At the end of this review, future trends for construction new types of electrochemical capacitor are proposed.

Combined UV-vis and quantum chemical studies of the structural flexibility and tautomerism of 6-R-3-hydroxy-2-pyrazine carboxamides in solutions revealed that their keto-enol transformations are accompanied by the deprotonation of enol tautomers and the formation of the corresponding anionic species. Both the solvent and the 6-R substituent strongly influence the relative abundance of the above forms in solutions. Anions are not formed in 1,2-dichloroethane (DCE), but the probability of deprotonation in neutral water and N,N-dimethylformamide (DMF) increases in the order R = H < F < NO2. Only enol tautomers of all solutes are found in DCE. DMF stabilizes keto forms only moderately and assists much strongly in the deprotonation of all three compounds. Water tends to stabilize both keto tautomers and deprotonated anions: the keto form dominates in the case of R = H (antiviral drug T-1105), the anions are found exclusively for R = NO2, and the aqueous solution of another antiviral drug, favipiravir (R = F), contains both the keto tautomer and the anionic form. The results of quantum chemical free energy calculations are in agreement with the experimental observations.

The escalating concentration of carbon dioxide in the atmosphere is a pressing environmental concern, necessitating the development of efficient technologies for CO2 reduction and utilization. In this context, metal-organic frameworks (MOFs) emerge as promising catalysts due to their tunable structures and unique chemical properties. This study focuses on the synthesis, characterization, and evaluation of amino-functionalized MOFs with cobalt and nickel nodes for the electrochemical reduction of CO2. Electrochemical investigations reveal that a cobalt-based MOF primarily facilitates the production of methane, demonstrating high selectivity and efficiency under controlled conditions. In contrast, a nickel-based MOF exhibits a broader array of reduction products, including methane, CO, and ethanol, with a significant conversion efficiency. These differences underscore the impact of the central metal node on the catalytic activity and product distribution. This comprehensive study not only advances our understanding of MOF-based catalysts for CO2 reduction but also underscores the significance of molecular engineering in enhancing the selectivity and efficiency of these processes. By demonstrating the potential of amino-functionalized MOFs with specific metal nodes, we contribute to the development of sustainable solutions for carbon capture and utilization, aligning with global efforts to mitigate climate changes and foster a green chemical industry. Integration of ferrocenyl and amine-functionalized MOFs enhances CO2 capture and reduction efficiency.