Organic Inorganic Hybrid Compound Research Articles

A new organic-inorganic hybrid compound based on sulfate: Structural characterization, DFT study, Hirshfeld analysis, and electrical, vibrational and thermal properties

This paper aims to study a new organo-sulfate (N(C2H5)4[HSO4][H2SO4]2) using X-ray diffraction, DFT, Hirshfeld surface analysis, thermal analysis, and IR, Raman, NMR, and impedance spectroscopy. The structure of this centrosymmetric compound with P21/c space group [Z = 4, a = 6.765(2) Å, b = 15.531(4) Å, c = 13.843(2) Å, β = 101.00(2)°] consists of (CH3CH2)4N+ cations, [HSO4]- anions, and bis sulfuric acid [H2SO4]2; the two sulfate species are linked via strong hydrogen bonds O–H⋯O and form (H2SO4.HSO4.H2SO4) trimmers. Hirshfeld surface analysis highlighted the predominance of O ….H/H⋯O contacts, as an indication of the strong hydrogen bonding in this compound. The IR (400–3600 cm−1) and Raman (50–3500 cm−1) spectra have been analyzed at room temperature. The bond lengths, angles, and theoretical frequencies of the optimized molecular geometry have been calculated using the DFT (B3LYP/6-31G(d)) method and compared to the experimental properties. This method represents the molecular structure and vibrational properties with reliable correlation coefficient values, calculated by the linear fitting, for distances (0.9963), angles (0.9833), and frequencies (0.9919).The 13C NMR spectrum shows two different carbon environments in the –CH2 and –CH3 groups. TGA-DTA analysis has shown that the adsorbed water molecules depart at 374 K and the crystal melts at 432 K. The electrical conductivity was measured using complex impedance spectroscopy in the frequency range of 1 kHz–13 MHz and temperature range of 313–363 K. The conductivity activation energies were calculated from the log(σT) and log(fp) curves at ΔEσ(LT) = 0.42eV and ΔEf(LT) = 0.40 eV. The conductivity relaxation parameters calculated from the M"/M"max curves (313–363K) reveal the H+ ion hopping process conduction in this material.

Cyclohexylammonium Hexaisothiocyanatonickelate(II) Dihydrate as a Single-Source Precursor for High Surface Area Nickel Oxide and Sulfide Nanocrystals

Cyclohexylammonium hexaisothiocyanatonickelate(II) dihydrate, (C6H11NH3)4[Ni(NCS)6]·2H2O, was synthesized, for the first time, by a four-step method in a yield of 95%. The compound was fully characterized by elemental microanalysis, Fourier transform infrared (FTIR), ultraviolet-visible-near infrared (UV-Vis-NIR), and nuclear magnetic resonance (NMR) spectroscopy and thermogravimetry. A single crystal X-ray diffraction (SXRD) gave the monoclinic space group P21/c with a = 15.8179 (5) Å, b = 10.6222 (3) Å, c = 13.8751 (4) Å, β = 109.362 (1)°, V = 2199.45 (11) Å3, Z = 2 (T = 293 K) for this novel hybrid organic–inorganic compound. The title compound was employed as a single-source precursor for the synthesis of mesoporous, high surface area nickel oxide (53 Å; 452 m2/g) and nickel sulfide (46 Å; 220 m2/g) via pyrolysis under air at 550 °C or helium atmosphere at 500 °C, respectively. X-ray powder diffraction (XRPD) demonstrated the nanocrystalline nature of both NiO and NiS with an average crystallite size of 16 and 54 nm, respectively. Scanning electron microscope (SEM) indicated the formation of agglomerated, quasi-spherical particles of nickel oxide and agglomerated flake-like structures of nickel sulfide. The high surface area, porosity, and nanocrystallinity of both NiO and NiS, obtained via this approach, are promising for a wide spectrum of applications.

Growth, crystal structure, Hirshfeld surface analysis, DFT studies, physicochemical characterization, and cytotoxicity assays of novel organic triphosphate.

A novel organic-inorganic hybrid compound, named (1-phenylpiperazinium) trihydrogen triphosphate, with the formula (C10H15N2)2H3P3O10 has been obtained by low speed of evaporation of a mixture of an alcoholic solution of 1-phenylpiperazine and triphosphoric acid H5P3O10 at room temperature after using the ion exchange chemical procedure. To carry out a detailed crystallographic structure analysis, single-crystal X-ray diffraction has been reported. In the molecular arrangement, the different entities are held together through N-H…O, O-H…O, and C-H…O hydrogen bonds, building up a three-dimensional packing. Powder X-ray diffraction analysis is acquired to confirm the purity of the product. The nature and the proportion of intermolecular interactions were investigated by Hirshfeld surface analysis. In order to support the experimental results, a density functional theory (DFT) calculation was performed, using the Becke-3-parameter-Lee-Yang-Parr (B3LYP) function with LANL2DZ basis set, and the data indicate much agreement between the experimental and the theoretical results. Thus, the physicochemical properties were studied employing a variety of techniques (FTIR, NMR, UV-visible, and photoluminescence). To get an insight of the possible employment of the present material in biology, cell viability assays were performed.

A New Organic–Inorganic Hybrid Compound: Synthesis, crystal structure, Hirshfeld surface analysis, vibrational, optical, magnetic properties and theoretical study

Renewable technologies represent a solution to reduce the energy demand and dependency on fossil fuels. Here, attention is focused on organic inorganic hybrids used in photovoltaic. The present work is the investigation of a new organic–inorganic hybrid C4H10Cl3NO2Sn that crystallizes in a monoclinic system with C2/c space group and unit cell parameters (a = 32.071(5) Å, b = 5.827(5) Å, c = 11.596(5) Å, β = 94.858(5) °, and Z = 4) at room temperature. The crystal structure exploration reveal the stabilization of the crystal packing is carried out by a complex network of hydrogen interactions that lead formation of layered organic- inorganic hybrid stacked along the a-axis. The intermolecular interactions were elucidated by Hirchfeld surface analysis and fingerprint plots. The vibration modes were probed by Micro-Raman spectroscopy. Also, the vibrating sample magnetometer (VSM) measurement shows the ferromagnetism aspect of the compound as well as the energy gap was estimated from UV–visible absorption spectroscopy.

Synthesis, crystal structure, structural phase transition and dielectric properties of new organic-inorganic hybrid compound: (C6H5CH2N(C2H5)3)CdCl3

Single crystal of new organic-inorganic hybrid compound, (C6H5CH2N(C2H5)3)CdCl3, was successfully synthesis by slow evaporation method at room temperature and characterized by divers techniques such as single X-ray diffraction, Infrared and Raman spectroscopy, Thermal analysis (TGA and DSC), Variable temperature X-ray powder diffraction (VT‒XRPD) and dielectric properties. The results of single X-ray studies demonstrated that the title compound crystallizes in the monoclinic system with the space group P21/n. The atomic arrangement of the crystal structure can be described as 1D polymeric inorganic chain CdCl5 along the a-axis between which the organic groups are located. It consists on isolated square-pyramidal [CdCl5]3− anions and triethylbenzylammonuim (C6H5CH2N(C2H5)3)+ cations, which are interconnected via C−H…Cl weak hydrogen bonds forming 3D network. Investigation of RT‒XRPD was carried out to identify the purity of the bulk material. Hirshfeld surface and fingerprint plots reveal that the structure is dominated by H…H and H…Cl/Cl…H contacts. It is found that the (C6H5CH2N(C2H5)3)CdCl3 material displays a irreversible structural phase transition at T = 413 K. This latter was confirmed by means of variable temperature X- ray powder diffraction and dielectric permittivity (ε′andε′).

Low-temperature synthesis of high-entropy (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O nanoparticles via polyol process

Functional high-entropy oxide (HEO) (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O has attracted great attention due to its unique properties. High temperature (∼1000 °C) sintering is generally required to form the single-phase (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O. In this work, a polyol process followed by quenching is established to synthesize (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O. Benefiting from the homogeneous distribution of metal elements in the inorganic-organic hybrid compound obtained from polyol process, a single-phase HEO can be achieved after quenching at 800 °C.

The first observation that metal chalcogenide supertetrahedral cluster is corner-coordinated by neutral amine group

Reported here is a new organic–inorganic hybrid compound {[(Ga10S17)(H+–AEP)2]·(H+–AEP)2} (1) with an one-chain structure and an unprecedented corner-coordination mode between the amine group from the 1-(2-aminoethyl)piperazine ligand and gallium ions in metal chalcogenide supertetrahedral cluster. This is the first observation that a metal chalcogenide supertetrahedral cluster is corner-coordinated by an amine group from alicyclic ammonia. The characterization of UV–Vis diffuse reflectance spectroscopy and optoelectronic properties on 1 indicated its potential application in semiconductor devices and photoelectric sensors.

Crystal structure of hexa-sodium tetra-serinolium paratungstate B deca-hydrate, [Na6{(CH2OH)2CHNH3}4][W12O40(OH)2]·10H2O.

The title polyoxometalate-based organic-inorganic hybrid compound, [Na6(C3H10NO2)4][W12O40(OH)2]·10H2O, consists of a di-μ 3-hydroxido-tetra-μ 3-oxido-octa-deca-μ-oxido-octa-deca-oxidododeca-tungstate (para-do-deca-tungstate B) anion, [W12O40(OH)2]10-, and six sodium cations coordinated by the oxygen ions of the polyanions, serinol ligands protonated at the N atom, and water mol-ecules. The centrosymmetric paratungstate B anion shows characteristic features in terms of bond lengths and angles. The three-dimensional framework structure is established by bonding of the sodium cations with oxygen ions of the paratungstate B anions and a network consisting of N-H⋯O and O-H⋯O hydrogen bonds of medium strength between the protonated serinol cations, water mol-ecules and the paratungstate B anions. The title compound was also characterized by means of elemental analysis, IR spectroscopy and thermogravimetric analysis.

Synthesis, structural and spectroscopic studies, DFT calculations, thermal characterization and Hirshfeld surface analysis of copper(II) organic-inorganic hybrid material (C12H22N2)[CuCl4

A new organic-inorganic hybrid compound, (C12H22N2)[CuCl4], has been synthesized by slow evaporation at room temperature and characterized using elemental analysis, powder X-ray diffraction, FT-IR, UV–Vis and mass spectroscopy. Single-crystal X-ray diffraction analysis indicates that the asymmetric unit in this compound consists of one tetrahedral [CuCl4]2- ion and one diprotonated organic cation (C12H22N2)2+, all of which lie in general positions. The crystal structure of the title salt is made up of mixed layers, formed by organic cations and inorganic anions, stacking along the b-axis. Crystal cohesion is achieved through N-H…Cl hydrogen bonds between organic cations and inorganic anions, and Cl…Cl interactions, building up a two-dimensional architecture. Thermal behavior (DTA/TGA) of this copper complex was also explored showing the different steps of weight loss. Hirshfeld surface analysis has been performed to investigate the intermolecular interactions and crystal packing of the title compound. Optical properties were recorded at room temperature using UV-visible spectroscopy in the spectral range 200-700 nm. The optical absorbance was measured to determine the optical band gap using Kubelka-Munk function. The electronic transition of the title complex was recorded in ethanol solvent and the electronic distribution of HOMO − LUMO was rationalized theoretically through density functional theory (DFT).

Metal regulated organic–inorganic hybrid ferroelastic materials: [(CH3)3CN(CH3)2CH2F]2[MBr4] (M = Cd and Zn)

Two organic–inorganic hybrid compounds [(CH3)3CN(CH3)2CH2F]2[MBr4] (M = Cd and Zn) undergo ferroelastic phase transitions. The substitution of metal center Cd with Zn of inorganic anions regulate the ferroelastic phase transitions.

(C3N6H7)2SiF6·H2O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent

A new organic–inorganic hybrid compound (C3N6H7)2SiF6·H2O, in which [C3N6H7]+groups are uniformly arranged under the regulation of SiF6octahedra, shows highly polarization anisotropy and a breakthrough in the energy gap.

Metal ion induced dual switchable dielectric and luminescent properties in hybrid halides.

A new multi-functional organic-inorganic hybrid compound was successfully obtained by regulating metal halides. Apart from excellent luminescence properties, in particular, the introduction of a Mn halide successfully achieved a dual-switchable dielectric property, which could lead to very interesting exploration in sensors.

Reentrant structural and optical properties of organic–inorganic hybrid metal cluster compound ((n-C4H9)4N)2[Mo6Bri8Bra6

A metal cluster-based inorganic–organic hybrid compound, (TBA)2[Mo6Bri8Bra6], exhibits a reentrant transition of the crystallographic structure and photoluminescence property in a low temperature range.

Two manganese chloride organic–inorganic hybrid compounds showing strong luminescence and switchable phase transition and dielectric anomaly

Two organic–inorganic hybrid manganese halide perovskite compounds [Me3NNH2]MnCl3 and [(CH3)3NCH2CH2F]2MnCl4 exhibit switchable phase transition and dielectric anomaly, and also emit strong red and green luminescence.

Materials today: Proceedings χ (3) measurement and second harmonic generation of organic–inorganic hybrid compounds headed for optoelectronic applications-L cysteine hydrogen orthoborate

Novel semi organic non-linear single crystal of L-cysteine hydrogen orthoborate was grown from aqueous solution by the slow evaporation technique at room temperature. The grown crystal was characterized by single crystal x-ray diffraction. The chemical composition of the crystal was identified by the energy dispersive x-ray analysis. The fourier transform infrared spectra were recorded to identify the functional groups presented in the sample. The transparency range of the material was analyzed by the UV–Vis-NIR measurements. The absorption studies showed that the UV cut-off wavelength to be at 224 nm. The transmission studies indicated a rapid and intensive transition at the cutoff wavelength. Crystals showed transparency in the entire visible region with 5.5 eV optical band gap and also showed an excellent second order nonlinear optical properties and third order susceptibilities. Z Scan measurements revealed the saturation absorption of the grown crystal. Such parameters as nonlinear refractive index, absorption coefficient and nonlinear optical susceptibility were determined. The thermal behavior of the grown crystal was analyzed by TG/DSC analysis, showed a major weight loss around 246 °C and that corresponds to the melting point of the sample that showed good thermal stability of the grown crystal. The laser damage threshold value for L-Cysteine hydrogen orthoborate was found to be 139 mJ/cm−2.

Stable two-dimensional lead iodide hybrid materials for light detection and broadband photoluminescence

We report here two new semiconducting two-dimensional lead iodide organic–inorganic hybrid compounds with broadband emission and strong photocurrent response.

Self-assembly of a new cobalt complex, (C6H14N2)3[CoCl4]Cl: Synthesis, empirical and DFT calculations

The aim of this work is the preparation and the crystallization of new organic–inorganic hybrid compound including cyclohexylamine and [CoCl4]2−, (C6H14N2)3[CoCl4]Cl. Our compound has been studied by single-crystal X-ray diffraction (XRD), IR and TG-DTA examination. The XRD investigation allows to structurally distinguish our material by its monoclinic system and P21/n space group through the lattice parameters a = 15.2645 (12) Å, b = 10.0843 (7) Å, c = 17.4450 (13) Å, β = 95.957 (3)° and Z = 4. The crystal arrangement shows inorganic entities of [CoCl4]2− and chloride spreading in (10 1-) plane which are connected to cyclohexylammonium cations via N(C)–H…Cl H-bonds. The experimental studies on the compound have been accompanied computationally by DFT calculations via the B3LYP functional. The intermolecular interactions using were quantitatively studied by 3D-HS coupled with two dimensional fingerprint (2D-FP) plots and analyzed by the RDG and AIM approaches. The electron localization function (ELF) investigation was performed to explain the chemical structure of (C6H14N2)3[CoCl4]Cl.

Low-dimensional compounds containing bioactive ligands. Part XVII: Synthesis, structural, spectral and biological properties of hybrid organic-inorganic complexes based on [PdCl4]2− with derivatives of 8-hydroxyquinolinium

In this study, four hybrid organic-inorganic compounds (8-H2Q)2[PdCl4] (1), (H2ClQ)2[PdCl4] (2), (H2NQ)2[PdCl4] (3) and (H2MeQ)2[PdCl4]·2H2O (4) (where 8-H2Q = 8-hydroxyquinolinium, H2ClQ = 5-chloro-8-hydroxyquinolinium, H2NQ = 5-nitro-8-hydroxyquinolinium and H2MeQ = 2-methyl-8-hydroxyquinolinium) were synthesized through organic cation modulation. Single-crystal X-ray structure analysis of compounds 1 and 3 indicates that their structures are planar and consist of [PdCl4]2− anions and 8-H2Q or H2NQ cations, respectively. Both ionic components are held together through ionic interactions and hydrogen bonds forming infinite chains linked through π-π interactions to form 2D structures. Furthermore, NMR spectroscopy, UV–Vis spectroscopy, elemental analysis, and FT-IR spectroscopy were used to explore the synthesized compounds. The DNA interaction, antimicrobial activity, antiproliferative activity, and radical scavenging effect of the compounds were evaluated. The hybrid compounds and their free ligands can interact with the calf thymus DNA via an intercalation mode involving the insertion of the aromatic chromophore between the base pairs of DNA; compound 1 has the highest binding affinity. Moreover, they have high antimicrobial efficacy against the tested 14 strains of microorganisms with minimum inhibitory concentration values ranging from <1.95 to 250 μg/mL. The antiproliferative activity of the compounds was investigated against three different cancer cell lines, and their selectivity was verified on mesenchymal stem cells. Compounds 1 and 2 displayed selective and high cytotoxicity against human lung and breast cancer cells and showed moderate cytotoxicity against colon cancer cells. Accordingly, they might be auspicious candidates for future pharmacological investigations in lung and breast cancer research.

Newly-Obtained Two Organic-Inorganic Hybrid Compounds Based on Potassium Peroxidomolybdate and Dicarboxypyridinic Acid: Structure Determination, Catalytic Properties, and Cytotoxic Effects of Eight Peroxidomolybdates in Colon and Hepatic Cancer Cells.

Two new organic-inorganic hybrid compounds containing dicarboxylic pyridine acids have been obtained and characterized. Both compounds are potassium oxidodiperoxidomolybdates with 2,6-dicarboxylicpyridine acid or 3,5-dicarboxylicpyridine acid moieties, respectively. The chemical formula for the first one is C14H7K3Mo2N2O18 denoted as K26dcpa, the second C7H4K1Mo1N1O11.5—K35dcpa. Their crystal structures were determined using single crystal (K26dcpa) or XRPD—X-ray powder diffraction techniques (K35dcpa). The purity of the compounds was confirmed by elemental analysis. Their thermal stability was determined with the use of non-ambient XRPD. In addition, they were examined by IR spectroscopy methods and catalytic activity studies were performed for them. Catalytic tests in the Baeyer–Villiger reaction and biological activity have been performed for eight compounds: K26dcpa, K35dcpa, and six peroxidomolybdates previously obtained by our group. The anti-proliferative activity of peroxidomolybdenum compounds after 24 h of incubation was studied in vitro against three selected human tumor cell lines (SW620, LoVo, HEP G2) and normal human cells (fibroblasts). The data were expressed as IC50 values. The structure of the investigated oxodiperoxomolybdenum compounds was shown to have influence on the biological activity and catalytic properties. It has been shown that the newly-obtained compound, K35dcpa, is a very efficient catalyst in the Baeyer–Villiger reaction. The best biological activity results were obtained for Na-picO (previously obtained by us), which is a very effective anti-cancer agent towards SW 620 colorectal adenocarcinoma cells.

Crystal structure and thermochromic behavior of the quasi-0D lead-free organic-inorganic hybrid compounds (C7H9NF)8M4I16 (M = Bi, Sb)

The quasi 0D lead-free thermochromic organic-inorganic hybrid single crystals (C7H9NF)8M4I16 (M = Bi, Sb) were synthesized by a conventional solvothermal reaction method. The crystal structures were analyzed using single crystal X-ray diffraction (SXRD). Interestingly, as the temperature increases, the (C7H9NF)8M4I16 (M = Bi, Sb) crystals exhibit a peculiar thermochromic phenomenon. In order to explore the phenomenon of thermochromism, temperature dependent ultraviolet−visible-near-infrared (UV–vis–NIR) absorption spectra were measured. The bandgaps of (C7H9NF)8Sb4I16 and (C7H9NF)8Bi4I16 at room temperature are 2.34 eV and 2.1 eV, respectively, and they gradually decrease as the temperature increases. Combined with ab initio molecular dynamics (AIMD), the reduction of the bandgap at higher temperature and the occurrence of thermochromism could be caused by the stronger electronic activity (thermal excitation). The thermochromic characteristics of these low-dimensional organic-inorganic hybrid metal halides will provide alternative materials for smart windows temperature sensors, visual thermometers, and daylight control glasses and beyond.