One-Dimensional Organic-Inorganic Material (C6H9N2)2BiCl5: From Synthesis to Structural, Spectroscopic, and Electronic Characterizations.

The new organic-inorganic compound (C6H9N2)2BiCl5 (I) has been grown by the solvent evaporation method. The one-dimensional (1D) structure of the allylimidazolium chlorobismuthate (I) has been determined by single crystal X-ray diffraction. It crystallizes in the centrosymmetric space group C2/c and consists of 1-allylimidazolium cations and (1D) chains of the anion BiCl52-, built up of corner-sharing [BiCl63-] octahedra which are interconnected by means of hydrogen bonding contacts N/C-H⋯Cl. The intermolecular interactions were quantified using Hirshfeld surface analysis and the enrichment ratio established that the most important role in the stability of the crystal structure was provided by hydrogen bonding and H···H interactions. The highest value of E was calculated for the contact N⋯C (6.87) followed by C⋯C (2.85) and Bi⋯Cl (2.43). These contacts were favored and made the main contribution to the crystal packing. The vibrational modes were identified and assigned by infrared and Raman spectroscopy. The optical band gap (Eg = 3.26 eV) was calculated from the diffuse reflectance spectrum and showed that we can consider the material as a semiconductor. The density functional theory (DFT) has been used to determine the calculated gap, which was about 3.73 eV, and to explain the electronic structure of the title compound, its optical properties, and the stability of the organic part by the calculation of HOMO and LUMO energy and the Fukui indices.

Fluorescein Hydrazide-Appended Metal-Organic Framework as a Chromogenic and Fluorogenic Chemosensor for Mercury Ions.

In this work, we prepared a fluorescein hydrazide-appended Ni(MOF) (Metal-Organic Framework) [Ni3(BTC)2(H2O)3]·(DMF)3(H2O)3 composite, FH@Ni(MOF). This composite was well-characterized by PXRD (powder X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), N2 adsorption isotherm, TGA (thermogravimetric analysis), XPS (X-ray photoelectron spectroscopy), and FESEM (field emission scanning electron microscopy). This composite was then tested with different heavy metals and was found to act as a highly selective and sensitive optical sensor for the Hg2+ ion. It was found that the aqueous emulsion of this composite produces a new peak in absorption at 583 nm, with a chromogenic change to a pink color visible to the naked eye upon binding with Hg2+ ions. In emission, it enhances fluorescence with a fluorogenic change to green fluorescence upon complexation with the Hg2+ ion. The binding constant was found to be 9.4 × 105 M-1, with a detection limit of 0.02 µM or 5 ppb. This sensor was also found to be reversible and could be used for seven consecutive cycles. It was also tested for Hg2+ ion detection in practical water samples from ground water, tap water, and drinking water.

Synthesis of Novel Tetra(µ3-Methoxo) Bridged with [Cu(II)-O-Cd(II)] Double-Open-Cubane Cluster: XRD/HSA-Interactions, Spectral and Oxidizing Properties.

A new double-open-cubane core Cd(II)-O-Cu(II) bimetallic ligand mixed cluster of type [Cl2Cu4Cd2(NNO)6(NN)2(NO3)2].CH3CN was made available in EtOH/CH3CN solution. The 1-hydroxymethyl-3,5-dimethylpyrazole (NNOH) and 3,5-dimethylpyrazole (NNH) act as N,O-polydentate anion ligands in coordinating the Cu(II) and Cd(II) centers. The structure of the cluster in the solid state was proved by XRD study and confirmed in the liquid state by UV-vis analysis. The XRD result supported the construction of two octahedral and one square pyramid geometries types around the four Cu(II) centers and only octahedral geometry around Cd(II) two centers. Interestingly, NNOH ligand acts as a tetra-µ3-oxo and tri-µ2-oxo ligand; meanwhile, the N-N in NNH acts as classical bidentate anion/neutral ligands. The interactions in the lattice were detected experimentally by the XRD-packing result and computed via Hirschfeld surface analysis (HSA). The UV-vis., FT-IR and Energy Dispersive X-ray (EDX), supported the desired double-open cubane cluster composition. The oxidation potential of the desired cluster was evaluated using a 3,5-DTB-catechol 3,5-DTB-quinone as a catecholase model reaction.

Single-Crystal-to-Single-Crystal Transformation of Hydrogen-Bonded Triple-Stranded Ladder Coordination Polymer via Photodimerization Reaction.

A one-dimensional hydrogen-bonded triple-stranded ladder coordination polymer [Cd(bpe)1.5(NO3)2(H2O)] (1) (where bpe = trans-1,2-bis(4-pyridyl)ethylene) containing three parallel C═C double bonds was synthesized. This compound undergoes photochemical [2 + 2] cycloaddition and produces rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) in up to 67% yield via Single-Crystal-to-Single-Crystal (SCSC) transformation. Triple-stranded ladder-like structures have never before displayed such a kind of SCSC transformation. Furthermore, photoirradiation of ground 1 produces rctt-tpcb in up to 100% yield in the solid state. On the basis of the alignment of three C═C olefinic bonds of bpe ligands in parallel, only two out of the three aligned bpe are expected to undergo [2 + 2] photodimerization. However, the quantitative yield from the solid-state photochemical [2 + 2] cycloaddition reaction has been achieved via grinding of crystals of 1 to a powder. The effects of grinding on photoreactivity of 1 were thoroughly studied using 1H NMR spectroscopy, thermogravimetric analysis (TGA), and Raman spectroscopy. These studies indicate that the molecular movements of the hydrogen-bonded ladders are reinforced due to the loss of coordinated water molecules and the further crystal repacking via bond-breaking/forming of the hydrogen-bonded assemblies during mechanical grinding. The 100% photodimerization of ground 1 shows that the grinding accelerates internal molecular motions of ladder structures within the crystals lattice. The solid-state photoluminescence of 1, before and after UV irradiation, was investigated at room temperature, both indicative of interesting luminescent properties.

{[2-Methyl-2-(phen-oxy-meth-yl)propane-1,3-di-yl]bis-(-oxy)}di-benzene.

The title compound, C23H24O3, was obtained in a one-step (60% yield) synthesis from 1,1,1-tris(hydroxymethyl)ethane. It features a tripodal ligand capable of complexing metal centres. One of the three conformations involving the methyl group, the central C-C bond and the phenoxy substituents is antiperiplanar while the two others are synclinal [the corresponding C-C-C-O torsion angles are -174.6 (1), -53.2 (2) and -47.3 (2)°]. In the crystal, C-H⋯O inter-actions link the molecules into [010] chains.

Synthesis and Oxygen Evolution Reaction Application of a Co-Cd Based Bimetallic Metal-Organic Framework.

In the realm of renewable energy technologies, the development of efficient and durable electrocatalysts is paramount, especially for applications like electrochemical water splitting. This research focuses on synthesizing a novel bimetallic metal-organic framework (BMMOF11) using earth-abundant elements, cobalt (Co) and cadmium (Cd). BMMOF11 showcases a distinctive structure with distorted octahedral chains of CoO and CdO, linked by benzene tricarboxylic acid (BTC). Our study primarily investigates the electrocatalytic efficiency of BMMOF11, particularly in water oxidation reactions. For practical analysis, BMMOF11 was anchored onto nickel foam, forming BMMOF11/NF, to evaluate its electrocatalytic properties. Electrochemical testing revealed that BMMOF11/NF begins water oxidation at an onset potential of 1.62 V versus RHE, demonstrating high activity with a lower overpotential of 0.4 V to achieve a current density of 10 mA/cm2 . Moreover, BMMOF11/NF maintained stable water splitting performance, sustaining a current density of approximately 70 mA/cm2 under a voltage of 1.9 V relative to RHE. These findings indicate that BMMOF11/NF is a promising candidate for large-scale electrochemical water splitting, offering a blend of high activity and stability.

N,N,N',N'-Tetra-methyl-ethylene-diammonium tetra-chlorido-zincate.

The asymmetric unit of the title compound, (C6H18N2)[ZnCl4], consists of one tetra-chlorido-zincate anion and two half-N,N,N'N'-tetra-methyl-ethylenedi-ammonium cations. Each of the two di-ammonium cations is located about an inversion center and one of them is disordered over two sets of sites in a 0.780 (17):0.220 (17) ratio. The Zn(II) atom has a slightly distorted tetra-hedral coordination environment. The cations and anions are connected via N-H⋯Cl hydrogen bonds into chains extending along [0-11].

µ-2,2'-Bipyrimidine-κ(4)N(1),N(1'):N(3),N(3')-bis-[iodido(triphenyl-phosphane-κP)copper(I)] dimethyl-formamide disolvate.

In the title binuclear centrosymmetric complex, [Cu(2)I(2)(C(8)H(6)N(4))(C(18)H(15)P)(2)]·2C(3)H(7)NO, the bis-bidentate 2,2'-bipyrimidine ligand bridges two copper(I) ions, each additionally bound to an iodide anion and a triphenyl-phosphane ligand in a distorted tetra-hedral N(2)IP geometry. The complex mol-ecules pack in columns parallel to [100] generating cavities occupied by dimethyl-formamide solvent mol-ecules. Weak C-H⋯I hydrogen-bonding inter-actions help to stabilize the crystal packing.

catena-Poly[[[aqua-(1,10-phenanthroline-κ²N,N')zinc]-µ-acetyl-ene-dicarboxyl-ato-κ²O¹:O²] monohydrate].

In the title complex, {[Zn(C4O4)(C12H8N2)(H2O)]·H2O}(n), the penta-coordinated Zn(II) ion is bound to two N atoms of the 1,10-phenanthroline ligand, two O atoms from two bridging acetyl-enedicarboxyl-ate anions and a water O atom in a distorted trigonal-bipyramidal geometry. The crystal structure is characterized by polymeric zigzag chains running parallel to [2-10] and is stabilized by O-H⋯O hydrogen bonds.

(Acetato-κO)(acetato-κO,O')bis-(1,3-diazinane-2-thione-κS)cadmium(II).

In the title complex, [Cd(CH(3)COO)(2)(C(4)H(8)N(2)S)(2)], the Cd(II) cation is coordinated by three acetate O atoms and two S atoms of Diaz [Diaz = 1,3-diazinane-2-thione = 3,4,5,6-tetra-hydro-pyrimidine-2(1H)-thione]. The Cd(II) coordination is augmented by one considerably longer Cd-O bond of 2.782 (3) Što a carboxyl-ate O atom. The resulting coordination polyhedron around the Cd(II) cations can be described as a highly distorted octa-hedron. The Diaz ligand and the acetate anions are linked by N-H⋯O hydrogen-bonding inter-actions.

A novel cyclic dinuclear gold(I) complex induces anticancer activity via an oxidative stress-mediated intrinsic apoptotic pathway in MDA-MB-231 cancer cells.

A new dinuclear cyclic gold(I) complex [Au2(DCyPA)2](PF6)2, 1, based on bis[2-(dicyclohexylphosphano)ethyl]amine (DCyPA) has been synthesized and characterized by elemental analysis, IR and NMR spectroscopy, and X-ray crystallography. In the dinuclear complex cation [Au2(DCyPA)2]2+, the two gold(I) ions are bridged by the ligand bis[2-(dicyclohexylphosphano)ethyl]amine (DCyPA) giving rise to a 16-membered ring centrosymmetric metallacycle. The cytotoxicity of the complex was evaluated against the triple-negative human breast cancer cells MDA-MB-231. In order to understand the mechanism of the cytotoxic behavior, a variety of assays, including Annexin V-FITC/Propidium iodide double staining, ROS production, and mitochondrial membrane potential and migration assays were carried out. The results indicated that complex 1 induced cytotoxicity via an oxidative stress-mediated intrinsic apoptotic pathway in MDA-MB-231 cancer cells.

Racemic methyl 3,10-dioxa-2-aza-tri-cyclo-[6.2.1.0]undecane-4-carboxyl-ate.

The structure of the racemic title compound, C(10)H(15)NO(4), consists of a tricyclic skeleton comprising a six-membered piperidine ring and five-membered isoxazolidine and tetra-hydro-furan rings. The piperidine ring adopts a distorted chair conformation, while the isoxazolidine and tetra-hydro-furan rings have envelope conformations.

Dibromidobis(N,N,N',N'-tetra-methyl-thio-urea-κS)cadmium(II).

In the title compound, [CdBr(2)(C(5)H(12)N(2)S)(2)], the Cd(II) atom lies on a twofold rotation axis. It exhibits a distorted tetra-hedral coordination environment defined by two S atoms of two tetra-methyl-thio-urea (tmtu) ligands and two bromide ions. The crystal structure is consolidated by C-H⋯N and C-H⋯S hydrogen bonds.

Diiodidobis(N,N,N',N'-tetra-methyl-thio-urea-κS)cadmium(II).

In the title compound, [CdI(2)(C(5)H(12)N(2)S)(2)], the Cd(II) ion is located on a twofold rotation axis and is coordinated in a distorted tetra-hedral mode by two iodide ions and by two tetra-methyl-thio-urea (tmtu) ligands through their S atoms. The crystal structure is stabilized by C-H⋯N and C-H⋯S hydrogen bonds.

Dichloridobis(N,N,N',N'-tetra-methyl-thio-urea-κS)mercury(II).

In the title compound, [HgCl(2)(C(5)H(12)N(2)S)(2)], the Hg(II) atom is located on a twofold rotation axis and is bonded in a distorted tetra-hedral coordination mode to two chloride ions and to two tetra-methyl-thio-urea (tmtu) mol-ecules through their S atoms. The crystal structure is stabilized by C-H⋯N and C-H⋯S hydrogen bonds.

Dicyanidobis(thio-urea-κS)cadmium(II) monohydrate.

In the title compound, [Cd(CN)(2)(CH(4)N(2)S)(2)]·H(2)O, the Cd atom lies on a twofold rotation axis and is bonded to two S atoms of thio-urea and two C atoms of the cyanide anions in a distorted tetra-hedral environment. The crystal structure is stabilized by N-H⋯N(CN), N-H⋯O, O-H⋯N and N-H⋯S hydrogen bonds.

Regioselective Synthesis of Chromones via Cyclocarbonylative Sonogashira Coupling Catalyzed by Highly Active Bridged-Bis(N-Heterocyclic Carbene)Palladium(II) Complexes.

The one-pot regioselective and catalytic synthesis of bioactive chromones and flavones was achieved via phosphine-free cyclocarbonylative Sonogashira coupling reactions of 2-iodophenols with aryl alkynes, alkyl alkynes, and dialkynes. The reactions are catalyzed by new dibromidobis(NHC)palladium(II) complexes. The new bridged N,N'-substituted benzimidazolium salts (L1, L2, and L3) and their palladium complexes C1, C2, and C3 were designed, prepared, and fully characterized using different physical and spectroscopic techniques. The molecular structures of complexes C1 and C3 were determined by single-crystal X-ray diffraction analysis. They showed a distorted square planar geometry, where the Pd(II) ion is bonded to the carbon atoms of two cis NHC carbene ligands and two cis bromido anions. These complexes displayed a high catalytic activity in cyclocarbonylative Sonogashira coupling reactions with low catalyst loadings. The regioselectivity of these reactions was controlled by using diethylamine as the base and DMF as the solvent.

Soft Heteroleptic N-Heterocyclic Carbene Palladium(II) Species for Efficient Catalytic Routes to Alkynones via Carbonylative Sonogashira Coupling.

N,N'-Substituted di-isopropyl (NHC-1), benzyl-isopropyl (NHC-2), and adamantyl-isopropyl (NHC-3) benzimidazolium salts react with palladium(II) bromide in pyridine to afford the corresponding trans-dibromidopyridinepalladium(II) complexes Pd-C1, Pd-C2, and Pd-C3 in high yields. A distorted square planar geometry for Pd-C2 and Pd-C3 was confirmed by single-crystal X-ray diffraction. The palladium(II) complexes show a remarkably higher catalytic activity and selectivity, compared to the literature data, in carbonylative Sonogashira coupling reactions of aryl iodides and aryl diiodides with aryl alkynes, alkyl alkynes, and dialkynes. Excellent yields with as low as 0.03 mol % loading of the catalyst were obtained. In the series of benzimidazolium (NHC) precursors, the 1H NMR signals of the α hydrogen show a consistent probing of the N-substituent donor strength. The density functional theory (DFT) quantum mechanical descriptors of the frontier orbitals were calculated. A linear correlation of the calculated absolute softness of the complexes versus the calculated percent buried volume (%V bur) of their corresponding ligands was obtained. The catalytic activity experimental data are consistent with the hard soft acid base (HSAB)-predicted high affinity of the softest Pd-C3 complex for soft substrates, such as aryl iodides.

Broad-band luminescence involving fluconazole antifungal drug in a lead-free bismuth iodide perovskite: Combined experimental and computational insights.

The synthesis and characterization of a lead-free perovskite-type material, (C13H14N6F2O)2 Bi2I10 is reported. It exhibits a zero-dimensional (0D) Bi2I104- octahedral unit, surrounded by a flexible tripodal antifungal ligand (H2Fluconazole)2+. The several intermolecular interactions of the independent cation and the bismuth iodide octahedra were tested via the Hirshfeld surface analysis. The detailed interpretation of the vibrational modes was carried out. The band gap (Eg) of 2.10 eV agrees with the theoretical values. Upon photoexcitation, the crystals exhibit a broadband green emission peaked at 534 nm, which originates from electronic transitions within the inorganic cluster [Bi2I10]4-. The theoretical calculations were carried out using DFT and TD-DFT methods to appraise the molecular geometry, vibrational spectra, electronic absorption spectra, frontier molecular orbitals (FOMs) and global reactivity descriptors. Calculations reveal that the energy gap (Eg) and other chemical reactivity descriptors are primarily linked to the inorganic anion and the triazolium rings (A and B) of the organic cation reflecting their importance in the activity and the antioxidant ability of the molecule.

2-Isoxazolidineethanols: an NMR study of the effect of intramolecular H-bonding on the population of nitrogen invertomers and inversion process.

A series of (betaR,5R)- and (betaR,5S)-2,5-disubstituted isoxazolidines: 5-(substituent)-beta-phenyl-2-isoxazolidineethanols, have been prepared by asymmetric nitrone cycloaddition reactions and their NMR spectra recorded over a wide range of temperatures. The spectra at low temperatures indicate the presence of the (betaR,5S) diasteromer almost exclusively as a single invertomer having trans disposition of the substituents at N(2) and C(5), while the (betaR,5R) diasteromer remained as a mixture of two interconverting invertomers in deuterated chloroform. The effect of H-bonding - intramolecular in CDCl(3) and intermolecular in CD(3)OD - on the population ratio of the invertomers and nitrogen inversion process has been investigated. The nitrogen inversion barriers are determined using complete line-shape analysis, and their dependence on solvent is discussed. Due to steric factor the trans-invertomers are found to be more stable than their cis counterparts.