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The development and technological applications of molecular spin systems require versatile experimental techniques to characterize and control their static and dynamic magnetic properties. In the latter case, bulk spectroscopic and magnetometric techniques, such as AC magnetometry and pulsed electron paramagnetic resonance, are usually employed, showing high sensitivity, wide dynamic range, and flexibility. They are based on creating a nonequilibrium state either by changing the magnetic field or by applying resonant microwave radiation. Another possible source of perturbation is a laser pulse that rapidly heats the sample. This approach has proven to be one of the most useful techniques for studying the kinetics and mechanism of chemical and biochemical reactions. Inspired by these works, we propose an inductive detection of temperature-induced magnetization dynamics as applied to the study of molecular spin systems and describe the general design and construction of a particular induction probehead, taking into account the constraints imposed by the cryostat and electromagnet. To evaluate the performance, several coordination compounds of VO2+, Co2+, and Dy3+ were investigated using low-energy pulses of a terahertz free electron laser of the Novosibirsk free electron laser facility as a heat source. All measured magnetization dynamics were qualitatively or quantitatively described using a proposed basic theoretical model and compared with the data obtained by alternating current magnetometry. Based on the results of the research, the possible scope of applications of inductive detection and its advantages and disadvantages in comparison with standard methods are discussed. [ABSTRACT FROM AUTHOR]

Combining different metals in coordination compounds is an efficient strategy to improve their various properties. Herein, mixed nickel–cobalt hexacyanoferrate (NixCoyHCF) microcubes of varying x : y molar ratios are synthesized via a co-precipitation route and comprehensively characterized to study their material and electrochemical properties. NixCoyHCF microcubes display the battery-type electrochemical energy storage mechanism in aqueous electrolytes. Among the samples, Ni1Co2HCF microcubes deliver the highest specific capacity of 134 mA h g−1 (1068 F g−1) at a specific current of 1 A g−1. This significant enhancement in the capacity indicates the synergistic and cooperative effects between Ni and Co sites in Ni1Co2HCF microcubes. The asymmetric supercapacitor device assembled with Ni1Co2HCF microcubes delivers an excellent energy density of 74.4 μW h cm−2 at a power density of 750 μW cm−2 and retains 87.7% of its initial capacity after 2000 cycles at a current density of 5 mA cm−2, indicating its robust structural integrity and electrochemical durability. This study highlights the promising potential of mixed-metal hexacyanoferrates as high-performance electrodes for aqueous supercapacitors. [ABSTRACT FROM AUTHOR]

Coordination compounds with slow magnetic relaxation are of great interest due to their magnetic bistability. Herein, three cobalt(II) coordination polymers, formulated as {[Co2(btca)(bpym)]·4H2O}n (1) and {[Co2(btca)(bpym)]·2DMF·2H2O}n (2), {[Co2(H2btca)2(bpym)]}n (3) (H4btca = 1,2,4,5-benzenetetracarboxylic acid; bpym = 2,2′-bipyrimidine), were solvothermally synthesized and magnetically characterized. Single-crystal structural analyses reveal that compounds 1 and 2 are Co2+ dimer-based one-dimensional (1D) and 2D coordination polymers, respectively, while compound 3 is a Co2+ chain-based 2D coordination polymer with a new topology. The Co2+ dimers and chains in these compounds are well magnetically isolated due to the bulk tetracarboxylic linker. Magnetic studies reveal that antiferromagnetic interactions exist between the Co2+ ions bridged by the bpym ligand. For 1, no relaxation behavior can be detected, suggesting the paramagnetic behavior of 1. Interestingly, alternating current (AC) magnetic measurements observed slow magnetic relaxation under a 1000 Oe field for 2 and 3. These results provide not only three cobalt(II) coordination polymers with varying topology and magnetic behaviors but also a pyrimidine–tetracarboxylic ligand platform for designing new slow magnetic relaxing coordination polymers. [ABSTRACT FROM AUTHOR]

This study provides a detailed investigation into the synthesis, characterization, and biological activities of the coordination compounds FePPHBZC, CoPPHBZC, and NiPPHBZC. These compounds were synthesized with high yields by reacting chloride salts of Iron, Cobalt, or Nickel with 2‐(pyridin‐2‐yl)phenol (PPH) and 1H‐benzimidazole‐2‐carboxylic acid (BZC) in a 1:1:1 ratio. Various techniques including spectroscopic (IR, UV–vis, mass spectra), elemental analysis, conductivity, magnetic, and thermal analyses confirmed the formation and structure of these coordination compounds. Density functional theory (DFT) calculations were used to study their electronic structure, stability, and reactivity. 3D modeling revealed hexacoordinated geometries for Fe and Co complexes and a tetrahedral coordination for the Ni complex. Analysis of the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and other reactivity parameters indicated changes in reactivity upon metal coordination. Molecular Electrostatic Potential (MEP) diagrams identified electron‐rich areas prone to nucleophilic attack, important for protein interactions during docking studies. Biological evaluations demonstrated that metal–ligand complexes exhibit enhanced antimicrobial, antioxidant, and anti‐inflammatory activities compared to individual ligands, with larger inhibition zones and higher inhibitory activity. Molecular docking studies showed strong interactions between metal–ligand complexes and target proteins, suggesting potential therapeutic applications. Among them, FePPHBZC exhibited the strongest interactions, followed by CoPPHBZC and NiPPHBZC, characterized by hydrogen bonding, ionic interactions, and other non‐covalent interactions, contributing to their enhanced stability and binding affinity. [ABSTRACT FROM AUTHOR]

The issue of heavy metal pollution is a critical global concern that requires urgent solution. However, conventional heavy metal adsorbents are too costly to be applied in large-scale engineering. In this study, adsorption behavior and mechanism of sintering red mud (RM-A) and bayer red mud (RM-B) for heavy metals were investigated to address the disposal of red mud as industrial waste and remediation of heavy metal pollution. Batch adsorption experiments were conducted to explore the adsorption performances of RM-A and RM-B under various conditions. Characterization of RM-A and RM-B before and after adsorption by XRD, FTIR and SEM-EDX was applied to investigate the specific adsorption behavior and mechanism. Adsorption experiments of both RM-A and RM-B fitted pseudo-second-order kinetic model and Langmuir isotherm model, with estimated maximum adsorption capacity of 21.96 and 25.19 mg/g for Cd2+, 21.47 and 26.06 mg/g for Cu2+ and 55.47 and 59.65 mg/g for Pb2+, respectively. Precipitation transformation of calcite was the primary adsorption mechanism for RM-A, whereas ion exchange of cancrinite, surface coordination compounds of hematite and minor precipitation transformation of calcite accounted for the adsorption mechanism for RM-B. Overall, RM-A and RM-B exhibited best adsorption performance for Pb2+, with RM-B showing greater adsorption capacity attributed to its higher specific surface area. This study compared the adsorption properties of RM-A and RM-B for the first time and demonstrated that both red muds can be effectively applied to remove heavy metals, thereby contributing to the sustainable industrial waste management and resourceful reuse. [ABSTRACT FROM AUTHOR]

This perspective highlights recent developments of the use of N-heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (cAACs) in alane and aluminum organyl chemistry. Especially in the last few years this flourishing research field led to some remarkable discoveries including various substitution patterns at the central aluminum atom, different oxidation states, neutral and charged compounds with varying coordination numbers and unique reactivities. Thereby NHCs play a vital role in the stabilization of these otherwise highly reactive compounds, which would not be realizable without the use of this intriguing class of ligands. Nevertheless, main group hydrides and especially NHC ligated alanes also tend to undergo NHC decomposition reactions, which are part of ongoing research and provide important information for NHC research in general. [ABSTRACT FROM AUTHOR]

π–π stacking interactions are versatile because they are involved in many processes, such as protein folding, DNA stacking, and drug recognition. However, from the point of view of crystal engineering, there is an incipient knowledge of its exploitation. A comparison of these interactions with hydrogen bonds shows a huge difference in their employment as a reliable non-covalent interaction. And different reasons can be listed to explain why hydrogen bonding can be considered a more robust interaction than π−π stacking. For instance, hydrogen bonds encompass a wide energy range (25–40 kJ mol−1). From this, these interactions can be classified as strong, moderate, and weak. Hence, the first two can be considered highly to moderately directional to be exploited in crystal engineering. This aspect is relevant for them to be used in a relatively reliably way in this area of supramolecular chemistry. On the other hand, in the case of π−π stacking, the energy range is 0–10 kJ mol−1, thus implying that hydrogen bonds or any other energetically more robust contact would predominate in the competition for establishing packing interactions in a given arrangement. In this sense, if stacking is pretended to be exploited from the point of view of crystal engineering, one of the points that must be ensured is that this interaction will be the one energetically predominant. However, although there are other factors to consider, it seems that energetics is the dominant one. In this line, our research group has obtained and studied many single-crystalline structures of coordination and organometallic compounds containing fluorinated thiolates. This being particularly true in the case of the thiolate 2,3,5,6-S(C6F4H-4) bound to different metals, where it has been observed that they preferentially tend to establish πF–πF stacking interactions, results that have been reported in several papers. Thus, from this perspective, we have explored, using ConQuest (CCDC) a number of structures to observe how feasible is to find stacking in coordination and organometallic compounds containing the thiolate 2,3,5,6-S(C6F4H-4). [ABSTRACT FROM AUTHOR]

The huge amount of urea applied has necessitated best-developed practices to slow down the release of nitrogen (N) fertilizer while minimizing nitrate loss. However, the impact of nitrification inhibitors on mineral-N turnover and the associated microbial mechanisms at different stages remains unknown. A 60-day incubation experiment was conducted with four treatments: no fertilizer (CK), urea (U), urea with copper pyrazole (UC), and urea coated with copper pyrazole (SUC), to evaluate the changes about soil ammonia N (NH4+ -N) and nitrate N (NO3--N) levels as well as in soil microbial community throughout the whole incubation period. The results showed that copper pyrazole exhibited significantly higher inhibition rates on urease compared to other metal-pyrazole coordination compounds. The soil NH4+ -N content peaked on the 10th day and was significantly greater in UC compared to U, while the NO3--N content was significantly greater in U compared to UC on the 60th day. Copper pyrazole mainly decreased the expression of nitrifying (AOB-amoA) and denitrifying (nirK) genes, impacting the soil microbial community. Co-occurrence network suggested that Mycobacterium and Cronobacter sakazakii-driven Cluster 4 community potentially affected the nitrification process in the initial phase, converting NH4+ -N to NO3- -N. Fusarium-driven Cluster 3 community likely facilitated the denitrification of NO3- -N and caused N loss to the atmosphere in the late stage. The application of copper pyrazole may influence the process of nitrification and denitrification by regulating soil microbial traits (module community and functional genes). Our research indicates that the addition of copper pyrazole alters the community function driven by keystone taxa, altering mineral-N turnover and supporting the use of nitrification inhibitors in sustainable agriculture. [ABSTRACT FROM AUTHOR]

Metal–organic framework materials, as innovative functional materials for nonlinear optical technologies, feature linear and nonlinear optical responses, such as a laser damage threshold, outstanding mechanical properties, thermal stability, and optical transparency. Their non-centrosymmetric crystal structure induces a higher-order nonlinear optical response, which guarantees technological applications. ZnII– and AgI–squarate complexes are attractive templates for these purposes due to their good crystal growth, optical transparency, high thermal stability, etc. However, the space group type of the catena-((μ2-squarato)-tetra-aqua-zinc(II)) complex ([Zn(C4O4)(H2O)4]) is debatable, (1) showing centro- and non-centrosymmetric monoclinic C2/c and Cc phases. The same is valid for the catena-((μ3-squarato)-(μ2-aqua)-silver(I)) complex (Ag2C4O4), (2) exhibiting, so far, only a C2/c phase. This study is the first to report new crystallographic data on (1) and (2) re-determined at different temperatures (293(2) and 300(2)K) and the non-centrosymmetric Cc phase of (2), having different numbers of molecules per unit cell compared with the C2/c phase. There are high-resolution crystallographic measurements of single crystals, experimental electronic absorption, and vibrational spectroscopic data, together with ultra-high-resolution mass spectrometric ones. The experimental results are supported for theoretical optical and nonlinear optical properties obtained via high-accuracy static computational methods and molecular dynamics, using density functional theory as well as chemometrics. [ABSTRACT FROM AUTHOR]

A motivating class of compounds with interest in the research field of biological active metallopharmaceuticals for cancer treatment is based on organometallic complexes of Sn(IV), exhibiting advantages such as improved cellular uptake and body excretion, lower toxicity, and fewer side effects compared to platinum-based drugs. In this study, the mononuclear organotin coordination complex [(CH3)2SnCl2(mebta)2] was synthesized and characterized using vibrational spectroscopy (IR, Raman), 1H NMR, 13C{1H} NMR, and X-ray crystallography. Its antiproliferative properties were thoroughly assessed across an aggressive triple-negative human breast cancer cell line. Notably, comparative studies with precursor materials verified that the observed biological activity is intrinsic to the complex itself. This study highlights the compound's ability to induce cell fate by disrupting essential cellular functions, such as proliferation. By exploring the antiproliferative effects of organotin(IV) derivatives, we introduce a novel class of Sn complexes with 1-methylbenzotriazole (mebta), demonstrating significant potential as promising antitumor agents in the field of organotin compounds. [ABSTRACT FROM AUTHOR]

The success of platinum-based chemotherapeutic drugs for clinical cancer treatments has inspired tremendous research efforts on developing new metallic anticancer agents with improved cytotoxic activity and reduced side effects. 2,2′;6′,2″-Terpyridine and its 4′-substituted derivatives have showed great potential as ligand compartments for designing new anticancer drug candidates involving base metals. In this work, we synthesized a series of cobalt and iron coordination compounds based on 4′-pyridyl-2,2′;6′,2″-terpyridine, including homoleptic complexes, a dinuclear bridged complex and 1- and 2-dimensional coordination polymers/networks. The polymorphism of two homoleptic CoII and FeII complexes has been described along with the structural characterization of a CoII coordination polymer and dinuclear FeIII complex by X-ray crystallography. These compounds were tested preliminarily as precatalysts for the regioselective hydrosilylation of styrene. Their cytotoxic activities against two human breast cancer cell lines (MCF-7 and MDA-MB 468) and a normal breast epithelial cell line (MCF-10A) were investigated in order to observe the best-performing drug candidates. [ABSTRACT FROM AUTHOR]

In the present work, we reported the synthesis and characterization [single crystal X-ray diffraction technique, spectroscopic, etc.] of two new Ni(II) and Zn(II) coordination compounds, viz. [Ni(2,6-PDC)2]2[Ni(en)2(H2O)2]2[Ni(en)(H2O)4]·4H2O (1) and [Zn(2,6-PDC)(Hdmpz)2] (2) (where 2,6-PDC = 2,6-pyridinedicarboxylate, en = ethylene-1,2-diamine, and Hdmpz = 3,5-dimethyl pyrazole). Compound 1 is found to crystallize as a multicomponent Ni(II) compound with five discrete complex moieties, whereas compound 2 is isolated as a mononuclear Zn(II) compound. A deep analysis of the crystal structure of 1 unfolds unusual dual enclathration of guest complex cationic moieties within the supramolecular host cavity stabilized by anion–π, π-stacking, N–H⋯O, C–H⋯O, and O–H⋯O hydrogen bonding interactions. Again, the crystal structure of compound 2 is stabilized by the presence of unconventional C–H⋯π(chelate ring) interactions along with C–H⋯O, C–H⋯N hydrogen bonding, π-stacking, and C–H⋯π(pyridyl) interactions. These non-covalent interactions were further studied theoretically using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, non-covalent interaction (NCI) plot index, and quantum theory of atoms in molecules (QTAIM) computational tools. The computational study displays that π-stacking or H bonds greatly tune the directionality of compound 1, although non-directional electrostatic forces dominate energetically. For compound 2, a combined QTAIM/NCI plot analysis confirms the presence of unconventional C–H⋯π(chelate ring) interactions along with other weak interactions obtained from the crystal structure analysis. Further, the individual energy contributions of these weak yet significant non-covalent interactions have also been determined computationally. [ABSTRACT FROM AUTHOR]

We synthesized four new copper(II) complexes with acetato and chlorido ligands and methylammonium (MA), dimethylammonium (DMA), and tetramethylammonium (TMA) counterions: (MA)4[Cu2Ac4Cl2]Cl2·2H2O (1), (DMA)2[Cu2Ac4Cl2] (2), (DMA)4[Cu2Ac4Cl2]Cl2·2H2O (3), and (TMA)5[Cu2Ac4Cl]Cl4·4H2O (4). All compounds were characterized by single-crystal X-ray diffraction, magnetic measurements, FTIR spectroscopy, and thermogravimetric analysis. Complexes 1, 2, and 3 consist of a dinuclear coordination anion [Cu2(Ac)4Cl2]2− with bridging acetato ligands arranged in a paddle-wheel conformation and square-pyramidal coordination around Cu(II) atoms, while the coordination anion in compound 4 is a polymeric chain, parallel to the c axis, with Cu2(Ac)4 units connected through bridging chlorido ligands. Magnetic measurements carried out between 2 K and 300 K indicate strong antiferromagnetic interactions between Cu(II) ions. The effective magnetic moments range from 1.94   μ B to 2.21   μ B , exceeding the spin-only value for Cu(II) ions ( μ e f f = 1.73   μ B ) and suggesting significant orbital contributions to the magnetic moment. Thermogravimetric analysis of all complexes showed a multistep decomposition behavior yielding elemental copper as the final product. [ABSTRACT FROM AUTHOR]

Three nickel, copper, and zinc complexes with dicarboxylic acids (3,3′-dithiodipropionic acid (H2dtdp) and fumaric acid (H2fu)) and N-donor ligands (1,10-phenanthroline (phen), N′–methyldipropylenetriamine (mdpta), and N,N,N′,N″,N″-pentamethyldiethylenetriamine (pmdien)) were synthesized. These complexes were characterized using elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Interestingly, [Ni(dtdp)(phen)(H2O)3]∙0.5H2O (1) is a mononuclear complex, where the dtdp dianion employs only one carboxylate group for coordination to the central nickel atom. [(ClO4)(mdpta)Cu(μ-dtdp)Cu(mdpta)(H2O)](ClO4) (2) is a dinuclear copper complex with a dtdp bridge and different coordination on the copper center. [{Zn(pmdien)(H2O)}2(μ-fu)](ClO4)2 (3) is a symmetric dimer with a bridging fumarate ligand. These coordination compounds were tested for their antibacterial activities on Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Enterococcus faecalis bacteria strains. All the complexes show moderate activities on the mentioned strains. [ABSTRACT FROM AUTHOR]

A rare pyrene‐based coordination compound of Hg(II) [Hg(L)2] (1) (where, HL=2‐((Pyren‐1‐ylmethylene)amino)benzenethiol) was synthesized and characterized by single crystal X‐ray diffraction (SC‐XRD) analysis. Crystallographic analysis revealed that complex 1 has seesaw geometry with HL coordinated as a bidentate ligand to a metal ion. The role of weak forces like π⋅⋅⋅π and CH⋅⋅⋅π interactions in influencing the self‐assembly process appears to be of importance. The electronic structure of the complex was predicted using DFT calculations with mixed basis set. DFT calculated structural parameters are in good agreement with the experimentally obtained parameters from XRD. Molecular reactivity and stability of the complex has been assessed through frontier molecular orbital analysis. Evaluation of molecular electrostatic potential (MEP) displays the electrophilic and nucleophilic reactivity sites. The Hirshfeld surface analysis clearly indicates C−H⋅⋅⋅π interactions and π⋅⋅⋅π stacking interactions are responsible to extend the supramolecular network of the complex. Analyses of the Finger print plots suggest that H⋅⋅⋅H and H⋅⋅⋅C contacts are major interactions for stabilizing the molecular crystal. [ABSTRACT FROM AUTHOR]

We report on the synthesis and characterization of Mn(III) chloride (MnIIICl3) complexes coordinated with N-oxide ylide ligands, namely trimethyl-N-oxide (Me3NO) and pyridine-N-oxide (PyNO). The compounds are reactive and, while isolable in the solid-state at room temperature, readily decompose into Mn(II). For example, "[MnIIICl3(ONMe3)n]" decomposes into the 2D polymeric network compound complex salt [MnII(µ-Cl)3MnII(µ-ONMe3)]n[MnII(µ-Cl)3]n·(Me3NO·HCl)3n (4). The reaction of MnIIICl3 with PyNO forms varied Mn(III) compounds with PyNO coordination and these react with hexamethylbenzene (HMB) to form the chlorinated organic product 1-cloromethyl-2,3,4,5,6-pentamethylbenzene (8). In contrast to N-oxide coordination to Mn(III), the reaction between [MnIIICl3(OPPh3)2] and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) resulted in electron transfer-forming d5 manganate of the [TEMPO] cation instead of TEMPO–Mn(III) adducts. The reactivity affected by N-oxide coordination is discussed through comparisons with other L–MnIIICl3 complexes within the context of reduction potential. [ABSTRACT FROM AUTHOR]

Coordination compounds of polydentate nitrogen ligands with metals are used extensively in research areas such as catalysis, and as models of complex active sites of enzymes in bioinorganic chemistry. Tris(2-pyridylmethyl)amine (TPA) is a tripodal tetradentate ligand that is known to form coordination compounds with metals, including copper, iron and zinc. The related compound, tris[(6- bromopyridin-2-yl)methyl]amine (TPABr3), C18H15Br3N4, which possesses a bromine atom on the 6-position of each of the three pyridyl moieties, is also known but has not been heavily investigated. The molecular structure of TPABr3 as determined by X-ray diffraction is reported here. The TPABr3 molecule belongs to the triclinic, P1 space group and displays interesting intermolecular Br...Br interactions that provide a stabilizing influence within the molecule. [ABSTRACT FROM AUTHOR]

The study focused on the nitrilo‐tris‐(methylene phosphonate) [K2ntpH4]2 and [(K1−yTly)2ntpH4]2 complexes, which are a series of isovalent substitutions. The crystals of [K2ntpH4]2 are monoclinic and belong to the space group of symmetry P21/c with Z=4. When thallium substitutes potassium, the molecular structure remains the same, but the symmetry of the crystal packing changes to a triclinic system, space group of symmetry P1‾ ${\bar{1}}$ , with Z=2. One coordination polyhedra maintains an isometric configuration, while the other undergoes significant distortions. Polarization‐selective coordination is observed, where the thallium(I) ion, which is easily polarizable, populates the highly distorted polyhedron. The low polarizable potassium ion populates the weakly distorted one. The crystal is formed with an average thallium fraction higher than the initial aqueous solution. This suggests that replacing potassium ions in the complex with thallium ions is energetically favourable. It could explain why thallium is toxic to intracellular enzymes and carriers of genetic information. The isovalent substitution of potassium made it possible to observe the step‐by‐step formation of a super‐strong hydrogen bond, a phenomenon that is rarely detected under normal conditions. The O...O interatomic distance in the hydrogen bond decreases gradually from 2.55 Å for [K2ntpH4]2 to 2.474 Å for [Tl2ntpH4]2. [ABSTRACT FROM AUTHOR]

Fourteen cobalt(II) complexes with the non-steroidal anti-inflammatory drugs sodium meclofenamate, tolfenamic acid, mefenamic acid, naproxen, sodium diclofenac, and diflunisal were prepared in the presence or absence of a series of nitrogen-donors (namely imidazole, pyridine, 3-aminopyridine, neocuproine, 2,2′-bipyridine, 1,10-phenanthroline and 2,2′-bipyridylamine) as co-ligands and were characterised by spectroscopic and physicochemical techniques. Single-crystal X-ray crystallography was employed to determine the crystal structure of eight complexes. The biological profile of the complexes was investigated regarding their interaction with serum albumins and DNA, and their antioxidant potency. The interaction of the compounds with calf-thymus DNA takes place via intercalation. The ability of the complexes to cleave pBR322 plasmid DNA at the concentration of 500 μM is rather low. The complexes demonstrated tight and reversible binding to human and bovine serum albumins and the binding site of bovine serum albumin was also examined. In order to assess the antioxidant activity of the compounds, the in vitro scavenging activity towards free radicals, namely 1,1-diphenyl-picrylhydrazyl and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), and their ability to reduce H2O2 were studied. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry," published by The Royal Society of Chemistry. It features articles and papers on various topics, including synthetic routes and chemical structural analysis for new Pt(II) metallodrug design and the synthesis and reactivity of air stable Ni(II) complexes. The correction notice in the document acknowledges an error in the original publication of a study on the reactivity of a Lewis superacidic carborane-based compound towards Lewis bases, authored by Libo Xiang, Alexander Matler, Leibo Tan, and Qing Ye. The notice provides the correct page number for the article. [Extracted from the article]

Methanol is being activelPTy investigated as a promising C1 reagent to replace conventional C1 reagents in organic synthesis, due to its properties of being economical, abundant, nontoxic and sustainably producible. However, because of the high enthalpy of dehydrogenation, it has not been reported frequently. Herein, we report that Pt single atoms (Pt1) and Pt clusters (Ptn) are cooperatively loaded on α-MoC to achieve the conversion of various of unsaturated N-containing compounds into value-added N-methylation compounds simply in methanol aqueous solution, successfully avoiding the use of external hydrogen or any additives. The synergy between coexisting Pt1 and Ptn on Pt1+n/α-MoC is identified as necessary to realize the tandem conversion with superior activity and selectivity. Pt1/α-MoC is the active site for in situ hydrogen production from aqueous phase methanol reforming, and Ptn/α-MoC is responsible for the successive hydrogenation and methylation. The partially positive Ptnδ+ species are crucial for the reductive N-methylation reaction, as the strong coordination of N-containing compounds to Pt particles (Ptn) significantly inhibits the catalytic activity. Experimental and DFT results further show that, unlike the traditional hydrogen-borrowing mechanism of methanol via the intermediate formaldehyde, formic acid is found to be a potent intermediate and agent for N-methylation. [ABSTRACT FROM AUTHOR]

A series of chelating N N proligands, 3‐(2‐pyridyl)‐5‐alkyl‐1,2,4‐triazoles (HLAlk), where alkyl=methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl was used as building blocks for designing of coordination compounds. Their reaction with an equimolar amount of [PdCl2(CH3CN)2] led to formation of series of six novel palladium complexes [Pd(HLAlk)Cl2], in which ligands are coordinated in the acid form. New proligands and Pd(II) complexes were characterized by IR, 1H and 13C NMR spectroscopy and elemental analysis. The Pd(II) complexes showed an unusual downfield shift in 1H NMR of the aliphatic proton that is the closest to triazole ring, which suggests the C−H...Cl hydrogen bonding, supported by X‐ray data for Pd(HLc−Pr)Cl2 and Pd(HLc−Bu)Cl2. [ABSTRACT FROM AUTHOR]

Coordination compounds of polydentate nitrogen ligands with metals are used extensively in research areas such as catalysis, and as models of complex active sites of enzymes in bioinorganic chemistry. Tris(2-pyridylmethyl)amine (TPA) is a tripodal tetradentate ligand that is known to form coordination compounds with metals, including copper, iron and zinc. The related compound, tris[(6-bromopyridin-2-yl)methyl]amine (TPABr3), C18H15Br3N4, which possesses a bromine atom on the 6-position of each of the three pyridyl moieties, is also known but has not been heavily investigated. The molecular structure of TPABr3 as determined by X-ray diffraction is reported here. The TPABr3 molecule belongs to the triclinic, P1 space group and displays interesting intermolecular Br···Br interactions that provide a stabilizing influence within the molecule. [ABSTRACT FROM AUTHOR]

Diazoalkenes readily react with tert‐butylphosphaalkyne (tBuCP) and white phosphorus (P4) to afford novel phosphorus heterocycles, 3H‐1,2,4‐diazamonophospholes and 1,2,3,4‐diazadiphospholes. Both species represent rare examples of neutral heterophospholes. The mechanism of formation and the electronic structures of these formal (3+2) cycloaddition products were analyzed computationally. The new phospholes form structurally diverse coordination compounds with transition metal and main group elements. Given the growing number of stable diazoalkenes, this work offers a straightforward route to neutral aza(di‐)phospholes as a new ligand class. [ABSTRACT FROM AUTHOR]

Two bidentate ligands (L1 = 1-pentyl-2-(pyridin-2-yl)-1H-benzimidazole and L2 = 1-heptyl-2-(pyridin-2-yl)-1H-benzimidazole) were employed for the synthesis of five mononuclear Fe(II) coordination compounds 1–5 containing perchlorate, tetrafluoroborate and triflate counterions. Single-crystal X-ray diffraction analysis confirmed the expected molecular structures of all the reported compounds, revealing a moderately distorted octahedral geometry of {FeN6} coordination chromophores. All five compounds exhibit thermal spin crossover with T1/2 temperatures allocated above 400 K. The theoretical calculations supported the experimental magnetic investigation and helped to explain the electronic structures of the reported complexes with respect to the occurrence of thermal spin state switching. In addition, compound 4 was employed for the preparation of Langmuir–Blodgett films and fabrication of molecular films using the method of spontaneous evaporation of the subphase. While the formation of Langmuir–Blodgett films was unsuccessful due to the instability of the compound at the water/air interface, the latter technique allowed the formation of molecular films of 4 with well-defined thickness and homogeneity. [ABSTRACT FROM AUTHOR]

The design of novel energetic compounds constitutes a pivotal research direction within the field of energetic materials. However, exploring the intricate relationship between their molecular structure and properties, in order to uncover their potential applications, remains a challenging endeavor. Therefore, employing multi-molecule assembly techniques to modulate the structure and performance of energetic materials holds immense significance. This approach enables the creation of a new generation of energetic materials, fueling research and development efforts in this field. In this study, a series of coordination compounds are synthesized by utilizing tetranitroethide (TNE) as an anion, which possesses a high nitrogen and oxygen content. The synthesis involves the synergistic modification between metal ions and small molecule ligands. Characterization of the obtained compounds is carried out using various techniques, including single crystal X-ray diffraction, IR spectroscopy, elemental analysis, and simultaneous TG–DSC analysis. Additionally, the energy of formation for these compounds is calculated using bomb calorimetry, based on the heat of combustion. The detonation performances of the compounds are determined through calculations using the EXPLO 5 software, and their sensitivities to external stimuli are evaluated. [ABSTRACT FROM AUTHOR]

Inorganic CsPbI3 perovskite has exhibited great application potential in perovskite solar cells (PSCs) due to its suitable optical bandgap and high chemical stability. However, the perovskite phases of CsPbI3 are not stable at room temperature, where they transition to non-perovskite phases. Humidity or water has been thought to be the primary factor inducing this phase transition, which should be avoided throughout the procedure of film and device processing. Surprisingly, the present study indicates that preparing a precursor solution in humid air is beneficial to the growth of high-quality CsPbI3 perovskite to enhance device performance. It is demonstrated that the incorporation of H2 O in the precursor solution from humid air or by intentional addition significantly changes the composition of coordination compounds and increases the amount of low iodine coordination complexes. As a result, the crystallization of dimethylammonium lead iodide (DMAPbI3) intermediate is suppressed well, which accelerates its subsequent conversion to CsPbI3 perovskite. Consequently, an oriented CsPbI3 perovskite film with improved crystallinity and lower defect density is obtained. Most importantly, carbon-based PSCs (C-PSCs) based on the CsPbI3 perovskite film achieve an efficiency of 16.05%, a new record for inorganic C-PSCs. [ABSTRACT FROM AUTHOR]

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The crystal structures of two coordination compounds, (acetato‐κO)(2,2′‐bipyridine‐κ2N,N′)(1,10‐phenanthroline‐κ2N,N′)copper(II) acetate hexahydrate, [Cu(C2H3O2)(C10H8N2)(C12H8N2)](C2H3O2)·6H2O or [Cu(bipy)(phen)Ac]Ac·6H2O, and (acetato‐κO)bis(2,2′‐bipyridine‐κ2N,N′)copper(II) acetate–acetic acid–water (1/1/3), [Cu(C2H3O2)(C10H8N2)2](C2H3O2)·C2H4O2·3H2O or [Cu(bipy)2Ac]Ac·HAc·3H2O, are reported and compared with the previously published structure of [Cu(phen)2Ac]Ac·7H2O (phen is 1,10‐phenanthroline, bipy for 2,2′‐bipyridine, ac is acetate and Hac is acetic acid). The geometry around the metal centre is pentacoordinated, but highly distorted in all three cases. The coordination number and the geometric distortion are both discussed in detail, and all complexes belong to the space group P. The analysis of the geometric parameters and the Hirshfeld surface properties dnorm and curvedness provide information about the metal–ligand interactions in these complexes and allow comparison with similar systems. [ABSTRACT FROM AUTHOR]

Luminescent CuI complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title Cu2I2P2S2‐type binuclear complex, di‐μ‐iodido‐bis[(thiourea‐κS)(triphenylphosphine‐κP)copper(I)], [Cu2I2(CH4N2S)2(C18H15P)2], conventionally abbreviated as Cu2I2TPP2TU2, where TPP and TU represent triphenylphosphine and thiourea, respectively, is described. In this complex, each CuI atom adopts a CuI2PS four‐coordination mode and pairs of atoms are connected to each other by two μ2‐I ligands to form a centrosymmetric binuclear cluster. It was also found that the paper‐based film of this complex exhibited obvious luminescence light‐up sensing for pyridine and 4‐methylpyridine. [ABSTRACT FROM AUTHOR]

A new coordination compound of Co(II) [Co(pydc)2](pydcH2)(Hapy)(H2O)5 (1) (where, pydcH2 = pyridine-2,6-dicarboxylic acid; Hapy = protonated 2- aminopyridine) was synthesized and characterized by single crystal X-ray diffraction (SC-XRD) analyses. Crystallographic analysis (CIF file CCDC no. 2236169) revealed that complex 1 has distorted octahedral geometry with pydc coordinated as a tridentate ligand to a metal ion. The electronic structure of the complex was determined using DFT calculations with pseudo potential of LANL2DZ basis function for Cobalt atom while B3LYP/GEN level using 6-31+G* basis set for other atoms. The optimized structure can reproduce the crystal structure with good accuracy at this computational level. Frontier molecular orbital analysis and molecular electrostatic potential (MEP) have been evaluated to understand the reactivity characteristics of the complex. Natural bond orbital analysis illustrates the charge transfer between the donor and acceptor sites of the investigated complex. Further, the intermolecular contacts of the complex areanalyzed through Hirshfeld surface analysis and finger print plots. [ABSTRACT FROM AUTHOR]

Two Co(II)-based coordination compounds, namely {[Co(apc)2]·H2O}n (1) and [Co(apc)2(H2O)2] (2), have been successfully prepared via reaction of a multifunctional ligand 2-aminopyrimidine-5-carboxylic acid (Hapc) with Co(NO3)2·6H2O based on different reaction environments. Both compounds were studied via elemental analysis (EA), single crystal X-ray diffraction analysis (SC-XRD), thermogravimetric analysis (TG), powder X-ray diffraction (PXRD) and infrared spectroscopy (IR). Fluorescence spectroscopy was employed to analyze the fluorescence properties of the ligand and the two compounds. The results revealed that the two compounds exhibited green and blue fluorescence, surpassing the original ligand in terms of properties. Based on the distinct fluorescence colors of the two compounds, there is potential to create multicolored fluorescent materials by adjusting their material ratios. This prospect could further extend their applications in the field of fluorescent materials. [ABSTRACT FROM AUTHOR]

Two complexes of Sn (IV), Sn (IV)‐TSC 1 and Sn (IV)‐TSC 2, with the ligands 4‐(2,4‐dimethylphenyl)‐1‐([pyridin‐2‐yl]methylene)thiosemicarbazide (TSC 1) and 4‐(2,5‐dimethoxyphenyl)‐1‐([pyridin‐2‐yl]methylene)thiosemicarbazide (TSC 2) were synthesized. X‐ray crystallographic investigation of Sn (IV)‐TSC 2 afforded valuable information on its octahedral geometry, monoclinic lattice and C 1 2/c 1 space group. The ligands are monoanionic tridentate via a deprotonated thiol sulfur atom and two nitrogen atoms of pyridine and azomethine moieties. These atoms coordinate tin alongside three independent chlorine atoms making the tin atoms in the complexes tetravalent, despite of incorporating tin (II) chloride in the reactions. Solutions of the ligands TSC 1 and TSC 2 (20 mg/ml in dimethyl sulfoxide) induced growth inhibitions only to Staphylococcus aureus (14 and 10 mm) and Escherichia coli (15 and 10 mm) bacteria. But the complexes displayed activities against four bacterial species, that is, S. aureus, E. coli, Bacillus subtilis and Pseudomonas aeruginosa (complex Sn (IV)‐TSC 1, complex Sn (IV)‐TSC 2 and ampicillin showed inhibition diameters with 12–14, 13–14 and 21–26 mm). All TSC ligands and coordination compounds induced cytotoxicity in MCF‐7 cancer and BHK normal cells. The compounds TSC 1, TSC 2, Sn (IV)‐TSC 1, Sn (IV)‐TSC 2 and doxorubicin inhibited the MCF‐7 (BHK) cells with IC50 values of 68.9 (126.6), 145.4 (110.6), 22.6 (16.7), 34.2 (16.1) and 9.66 (36.42) μM, respectively. [ABSTRACT FROM AUTHOR]

A new complex of copper(II) with methyl-5-(trifluoromethyl)pyrazol-3-yl-ketazine (H2L) was synthesized with the composition [Cu2L2]∙C2H5OH (1). Recrystallization of the sample from DMSO yielded a single crystal of the composition [Cu2L2((CH3)2SO)] (2). The coordination compounds were studied by single-crystal X-ray diffraction analysis, IR spectroscopy, and static magnetic susceptibility method. The data obtained indicate that the polydentate ligand is coordinated by both acyclic nitrogen and heterocyclic nitrogen atoms. The cytotoxic activity of the ligand and complex 1 was investigated on human cell lines MCF7 (breast adenocarcinoma), Hep2 (laryngeal carcinoma), A549 (lung carcinoma), HepG2 (hepatocellular carcinoma), and MRC5 (non-tumor lung fibroblasts). The complex was shown to have a pronounced dose-dependent cytotoxicity towards these cell lines with LC50 values in the range of 0.18–4.03 μM. [ABSTRACT FROM AUTHOR]

The reaction of 2-(1H-pyrrol-1-yl)ethanol with 3-hydroxyflavone in the presence of copper(II) bromide yielded a dimeric copper(II) complex, [μ-O-(κ2-O,O-flav)(κ2-N,O-2PEO)Cu]2 (1) (flav = 3-hydroxyflavonolate; 2PEO = 2-(1H-pyrrol-1-yl)ethanolate) with both the flav and 2PEO ligands bound to the copper(II) atom in a κ2-bonding mode. The dimer is held electrostatically by bridging oxygen atoms between two copper atoms. Complex 1 was characterized by single-crystal X-ray diffraction, infrared, and UV-Vis spectroscopy, elemental analysis, and melting point determination. The complex crystallizes in the monoclinic space group P21/n (14) with cell values of a = 11.85340(10) Å, b = 8.51480(10) Å, c = 23.8453(2) Å; β = 99.3920(10)°. [ABSTRACT FROM AUTHOR]

The medicinal properties of transition metal complexes are greatly influenced by the nature and physico-chemical features of the ligand present in the complex structure. Due to the unique biological properties of the organoselenium compounds reflected in the variety of pharmacological activities (such as antioxidative, antiviral, antimicrobial and anticancer), the last years have brought increased interest for their use as a ligands compounds in the design and syntheses of range of transition metal-based coordination compounds that have been explored as antitumor and antimicrobial agents. Our aim in this review is to provide the overview of an recent development of the transition metal complexes bearing organoselenium ligands in the structure that could be promising choice for the treatment of various diseases, particularly cancer and infective diseases. For this purpose, the complexes of Co, Ni, Cu, Zn, Ru, Pd, Pt, Au and Sn as the most explored examples will be included and discussed. [ABSTRACT FROM AUTHOR]

A polymeric coordination compound [Zn2(PABA)2(H2O)2Cl2]n (1) (where PABA is para-aminobenzoic acid) has been synthesized and characterized. We examined and explicated the porosity of the compound and employed a low-temperature nitrogen adsorption technique at 77 kelvins. Throughout the experiments, the nitrogen partial pressure ranged from 0.005 to 0.995 P/P0, aligning with the nitrogen adsorption and desorption curves. The surface area (SBET) was found to be 1945.72 m2/g with a micropore area of 361.56 m2/g that ensures the material's ability to effectively adsorb small molecules. The nitrogen adsorption behavior on this compound is not only facilitates a deeper comprehension of its textural and structural attributes but also unveils potential applications, especially in pharmaceutical domains. Additionally, Hirschfeld surface analysis was performed, yielding interatomic interaction percentages on the Hirschfeld surface. [ABSTRACT FROM AUTHOR]

Two new europium coordination compounds, [Eu2(papip)2(PhCOO)6] and [Eu2(phpip)2(PhCOO)6] (papip is 1-phenyl-2-(4-aminophenyl)imidazo[4,5-f][1,10]phenanthroline and phpip 1-phenyl-2-(4-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), have been synthesized hydrothermally and structurally characterized, involving the in situ hydrolysis of phenylacetonitrile to phenylacetate. The –NH2 group in the former complex was unexpectedly generated from the –NO2 group of free 1-phenyl-2-(4-nitrophenyl)imidazo[4,5-f][1,10]phenanthroline during the reaction process, representing the first such transformation in a hydrothermal reaction. Both complexes exhibit bright red photoemission typical of Eu(III) f–f transition under UV excitation, with long excited state lifetimes and quite high photoluminescence quantum yields. [ABSTRACT FROM AUTHOR]

Four novel Co(II) coordination compounds 1–4 of the general formula [Co(Ln)2][Co(NCY)4]·mCH3CN (where Ln are tridentate ligands L1 = 2,6-bis(1-hexyl-1H-benzimidazol-2-yl)pyridine for 1 and 2; L2 = 2,6-bis(1-octyl-1H-benzimidazol-2-yl)pyridine for 3; L3 = 2,6-bis(1-dodecyl-1H-benzimidazol-2-yl)pyridine for 4, Y = O for 1, 3, and 4 and Y = S for 2; m = 0 for 1 and 3, m = 0.5 for 2 and m = 2 for 4) were prepared and characterised. The molecular structures of all four compounds consist of the hexacoordinate complex cation [Co(Ln)2]2+ and tetracoordinate complex anion [Co(NCY)4]2−, with distorted octahedral and tetrahedral symmetry of coordination polyhedra, respectively. The electronic structures of all compounds feature an orbitally non-degenerate ground state well-separated from the lowest excited state, which allows the analysis of the magnetic anisotropy by the spin Hamiltonian model. ZFS parameters, derived from both CASSCF-NEVPT2 calculations and magnetic data analysis, indicate that tetrahedral anions [Co(NCY)4]2− exhibit small axial parameters ‖D‖ spanning the range of 2.2 to 7.7 cm−1, while octahedral cations [Co(Ln)2]2+ display significantly larger ‖D‖ parameters in the range of 37 to 95 cm−1. For 1–3, the Fourier-transform infrared magnetic spectroscopy (FIRMS) revealed a reasonable transmission with a magnetic absorption around the expected value for the ZFS accompanied by features allowing to identify phonon frequencies and simulate spin-phonon couplings. Dynamic magnetic investigations unveiled the field-induced slow relaxation of magnetisation, with maximal relaxation times (τ) of 92(2) μs for 2 at 2 K and BDC = 0.3 T. The temperature evolution of τ was analysed using a combination of Orbach, direct and Raman relaxations (Ueff = 8(1) K (5.6 cm−1)) or Orbach, direct and spin-phonon induced relaxations (Ueff = 10.3(9) K (7.2 cm−1)). The rest of the complexes, namely 1, 3, and 4 show field-induced slow relaxation of magnetisation with τ smaller than 16 μs. [ABSTRACT FROM AUTHOR]

Nickel coordination compounds featuring Ni–O bonds are key structural motifs in both bioinorganic and synthetic chemistries. They serve as precursors for organic substrate oxidation and are commonly invoked intermediates in water oxidation and oxygen reduction schemes. Herein, we disclose a series of well-defined dinuclear nickel complexes that, upon treatment with CO2 and H2O2, afford the first nickel-bound peroxycarbonate. This unprecedented nickel–oxygen intermediate is stabilized by hydrogen bonding templated across the bimetallic core. Contrasting copper and iron analogues, the nickel peroxycarbonate reversibly dissociates H2O2, a process that is shown to be accelerated by exogenous CO2. [ABSTRACT FROM AUTHOR]

Triple-negative breast cancer (TNBC), accounting for 15–20% of all breast cancers, has one of the poorest prognoses and survival rates. Metastasis, a critical process in cancer progression, causes most cancer-related deaths, underscoring the need for alternative therapeutic approaches. This study explores the anti-migratory, anti-invasive, anti-tumoral, and antimetastatic effects of copper coordination compounds Casiopeína IIIia (CasIIIia) and Casiopeína IIgly (CasIIgly) on MDA-MB-231 and 4T1 breast carcinoma cell lines in vitro and in vivo. These emerging anticancer agents, mixed chelate copper(II) compounds, induce apoptosis by generating reactive oxygen species (ROS) and causing DNA damage. Whole-transcriptome analysis via gene expression arrays indicated that subtoxic concentrations of CasIIIia upregulate genes involved in metal response mechanisms. Casiopeínas® reduced TNBC cell viability dose-dependently and more efficiently than Cisplatin. At subtoxic concentrations (IC20), they inhibited random and chemotactic migration of MDA-MB-231 and 4T1 cells by 50–60%, similar to Cisplatin, as confirmed by transcriptome analysis. In vivo, CasIIIia and Cisplatin significantly reduced tumor growth, volume, and weight in a syngeneic breast cancer model with 4T1 cells. Furthermore, both compounds significantly decreased metastatic foci in treated mice compared to controls. Thus, CasIIIia and CasIIgly are promising chemotherapeutic candidates against TNBC. [ABSTRACT FROM AUTHOR]

In this work, energetic coordination compounds (ECCs) of transition metals (Fe, Ni, Cu, Zn) containing aliphatic amines as ligands were synthesized: ethylenediamine; 1,3-diaminopropane; tris(2-aminoethyl)amine; tris(3-aminopropyl)amine. The compounds were investigated in terms of ignition/explosion temperature, friction and impact sensitivity. For selected compounds, structural characterisation was presented (IR-ATR spectroscopy, Raman spectroscopy) and their morphology was determined (SEM, powder XRD). They were also investigated by differential scanning calorimetry (DSC). In order to assess the potential application of selected ECCs in detonators, underwater explosion tests were carried out, determining energetic performance. The results achieved for detonators containing ECCs were compared with those for reference detonators (containing pentaerythritol tetranitrate, PETN), indicating their potential use as a "green" alternative to nitric acid esters. [ABSTRACT FROM AUTHOR]

The eleven new copper(II) and nickel(II) coordination compounds [Cu(L)Br]2 (1), [Cu(L)Cl] (2), [Cu(L)NO3] (3), [Ni(L)Cl] (4), [Ni(HL)2](NO3)2 (5), and [Cu(A)(L)]NO3, where A is 1,10-phenanthroline (6), 2,2′-bipyridine (7), 3,4-dimethylpyridine (8), 3-methylpyridine (9), pyridine (10) and imidazole (11) were synthesized with 3-(morpholin-4-yl)propane-2,3-dione 4-allylthiosemicarbazone (HL). The new thiosemicarbazone was characterized by NMR and FTIR spectroscopy. All the coordination compounds were characterized by elemental analysis and FTIR spectroscopy. Also, the crystal structures of HL and complexes 1, 6, 7, and 11 were determined using single-crystal X-ray diffraction analysis. Complex 1 has a dimeric molecular structure with two bromide bridging ligands, while 6, 7, and 11 are ionic compounds and comprise monomeric complex cations. The studied complexes manifest antibacterial and antifungal activities and also have an antiradical activity that, in many cases, surpasses the activity of trolox, which is used as a standard antioxidant in medicine. Copper complexes 1–3 have very weak antiradical properties (IC50 > 100 µM), but nickel complexes 4–5 are strong antiradicals with IC50 values lower than that of trolox. The mixed ligand copper complexes with additional ligand of N-heteroaromatic base are superior to complexes without these additional ligands. They are 1.4–5 times more active than trolox. [ABSTRACT FROM AUTHOR]

Carbon nitrides can form coordination compounds or metallic oxides in the presence of transition metals, depending on the reaction conditions. By adjusting the pH to basic levels for mild synthesis with metals, composites like g-C3N4-M(OH)x (where M represents metals) were obtained for nickel (II) and manganese (II), while copper (II) yielded coordination compounds such as Cu-g-C3N4. These materials underwent spectroscopic and electrochemical characterization, revealing their photocatalytic potential to generate superoxide anion radicals—a feature consistent across all metals. Notably, the copper coordination compound also produced significant hydroxyl radicals. Leveraging this catalytic advantage, with band gap energy in the visible region, all compounds were activated to disinfect E. coli bacteria, achieving total disinfection with Cu-g-C3N4. The textural properties influence the catalytic performance, with copper's stabilization as a coordination compound enabling more efficient activity compared to the other metals. Additionally, the determination of radicals generated under light in the presence of dicloxacillin supported the proposed mechanism and highlighted the potential for degrading organic molecules with this new material, alongside its disinfectant properties. [ABSTRACT FROM AUTHOR]

Two dinuclear double oxygen-bridged iron(III) complexes made of the Fe2(μ2-OR)2 diamond-core cluster resulting from the coordination between iron(III) cations with calix[4]arene ligands and bearing two lower-rim-appended salicylideneamine (4) or o-methoxy-salicylideneamine coordinating sites (5), connected to the macrocyclic platform via three methylene bridges and displaying a salen-type coordination pocket, were synthesized and characterized using single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), high-resolution mass spectrometry (HRESI-MS), IR, TG-DSC and EA techniques. Independent of the presence of the o-methoxy group in the salicylideneamine moieties, the as-formed complexes contained two nonequivalent iron(III) atoms, both adopting a distorted octahedral coordination N2O4-environment but differing in the cis and trans positions of the nitrogen atoms within the metal coordination sphere, as attested by single-crystal X-ray diffraction and DFT-B3LYP calculations. The possible reason for the observed coordination mode of the macrocyclic ligands is their conformational behavior upon coordination with Fe(III) cations, as confirmed by DFT-B3LYP analysis. 57Fe Mössbauer spectroscopy study showed that both Fe(III) atoms were present in high spin states at room temperature and at 80 K in the studied coordination compounds. The methoxy groups located at the ortho position of the salicylideneamine coordinating fragments were observed to influence the energy of the frontier orbitals, resulting in an increase in the bandgap energy from 1.97 eV to 2.07 eV, as experimentally established by solid-state voltammetry study of 42-Fe2 exp and 52-Fe2 exp, respectively. The interplay between the steric and electronic factors, emerging from the o-methoxy group within coordinating salicylideneamine moieties, seemed to have a negligible effect on the electronic properties of the prepared clusters but significantly impacted the frontier orbital energy distribution, according to both experimental data and theoretical calculations. [ABSTRACT FROM AUTHOR]

In this work, we report on five novel coordination polymers (CPs) based on the linkage of the [Cd(6apic)2] building block [where 6apic = 6-aminopicolinate] by different bipyridine-type organic spacers, forming different coordination compounds with the following formulae: [Cd(μ-6apic)2]n (1), {[Cd(6apic)2(μ-bipy)]·H2O}n (2), {[Cd(6apic)2(μ-bpe)]·2H2O}n (3), [Cd(6apic)(μ-6apic)(μ-bpa)0.5]n (4) and {[Cd2(6apic)4(μ-tmbp)]·7H2O}n (5) [where bipy = 4,4′-bipyridine, bpe = 1,2-di(4-pyridyl)ethylene, bpa = 1,2-di(4-pyridyl)ethane (bpa) and tmbp = 1,3-di(4-pyridyl)propane]. Most of the synthesized compounds form infinite metal–organic rods through the linkage of the building block by the bipyridine-type linker, except in the case of compound 4 whose assembly forms a densely packed 3D architecture. All compounds were fully characterized and their photoluminescence properties were studied experimentally and computationally through density functional theory (DFT) calculations. All compounds display, upon UV excitation, a similar blue emission of variable intensity depending on the linker employed for the connection of the building units, among which compound 2 deserves to be highlighted for its room temperature phosphorescence (RTP) with an emission lifetime of 32 ms that extends to 79 ms at low temperature. These good photoluminescence properties, in addition to its stability in water over a wide pH range (between 2 and 10), motivated us to study compound 2 as a sensor for the detection of metal ions in water, and it showed high sensitivity to Fe3+ through a fluorescence turn-off mechanism and an unspecific turn-on response to Zn2+. Furthermore, the compound is processed as a paper-based analytical device (PAD) in which the phosphorescence emission is preserved, improving the sensing capacity toward Fe3+ ions. [ABSTRACT FROM AUTHOR]

The crystal structure of the title solvated coordination compound, [Co (SCN)4 (BtaH)2]·(BtaH)2.6(H2O), consists of discrete complexes in which the Co2+ cations are sixfold coordinated by four N-bonded thiocyanate anions and two 1-H benzotriazolium molecules to generate distorted trans-CoN6 octahedra. The discrete entities are each connected by three solvate molecules into chains via strong O—H···N hydrogen bonds. These chains are further linked by additional O—H···N, N—H···O, N—H···S, O—H···S and O—H···O hydrogen bonds into a three-dimensional network. Within this network, channels are formed that propagate along the c-axis direction and embed additional acetonitrile solvent molecules that are hydrogen-bonded to the network. In addition, density functional theory (DFT) calculations using the M06-2X/gen method were used to study the system's electronic properties. Interestingly, molecular docking and topological analyses were performed on compounds against various target anti-inflammatory receptors to investigate which targets exhibit the best binding affinities and hydrogen-bonding interactions. Done. As a result, it exhibits excellent anti-inflammatory activity, making it a suitable drug candidate for inflammatory diseases. [ABSTRACT FROM AUTHOR]