Organic Inorganic Hybrid Compound Research Articles

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.

Crystal structure, vibrational spectra, optical properties and thermal behavior of the 1D perovskite (2-amino-4-methylpyridinium)trichlorocadmate(II) (C6H9N2)1 ∞[CdCl3

The organic-inorganic hybrid compound (2-amino-4-methylpyridinium) trichlorocadmate(II), (C6H9N2)1 ∞[CdCl3] was prepared in crystalline form by solvent evaporation at room temperature. Infrared and Raman spectra allowed tracing the entities of the organic aromatic cation and the inorganic 1 ∞CdCln scaffold. X-ray diffraction showed that the compound crystallizes in the orthorhombic system in the centrosymmetric space group Pnma and has a one-dimensional (1 D) perovskite structure. Hirshfeld surface analyses (d norm and shape index) of the studied structure, as well as its fingerprints, allowed us to identify and quantify the intermolecular interactions such as H bonds and π stacking. UV-visible absorption spectroscopy allowed us to estimate the direct band gap using the Tauc-extrapolation method. From this, we conclude a semiconducting character of the compound with a band gap of about 3.5 eV. Photoluminescence was observed with maxima at 351 and 388 nm when excited at 312 nm and can be traced to excited π–π* states in the organic cation. Thermogravimetric and differential thermal analysis showed that the compound is stable up to 200 °C and decomposes stepwise.

Synthesis and characterization of a new organic-inorganic hybrid material based on antimony

In the current research work, a new organic–inorganic hybrid compound of the formula [C3H5N2S] SbCl4 was successfully synthesized and characterized, where C3H5N2S stands for the cation of 2-aminothiazole. The synthesis was carried out by slow evaporation of raw materials and colourless good-quality crystals were obtained. The single crystal X-ray diffraction analysis of the crystals demonstrated a 0-dimension structure consisting of Sb2Cl8 dimers separated by 2-aminothiazolecations. The cohesion and stabilization between these entities is performed via N-H···Cl hydrogen bonds. The samples were characterized also by Powder X-ray Diffraction (PXRD) analysis. The functional groups in the complex were confirmed by Fourier transform IR (FT-IR) and Fourier transform Raman (FT-Raman) spectroscopies. Thermogravimetric analysis (TGA) was performed to examine the phase transition, degradation and thermal stability of the material. Optical absorption measurements revealed two absorption bands located at 263 and 234 nm (4.7 and 5.3 eV). The Nuclear Magnetic Resonance (NMR) spectrum goes in good consistency with the X-ray structure.

Synthesis, crystallographic structure, DFT computational studies and Hirschfeld surface analysis of a new tetranuclear anionic bromobismuthate(III): [C12H20N2]2Bi4Br16•2H2O

• A new tetranuclear anionic bromobismuthate [C12H20N2]2Bi4Br16•2H2O was synthesized and characterized. • The X-ray crystal structure of this new complex was elucidated. • Intermolecular interactions were analyzed by Hirshfeld surface analysis. • The electrostatic potentials of the equilibrium geometry and the molecular HOMO-LUMO have been investigated. • Proton affinities, relative stabilities and the relative energies have been studied using the density functional theory (DFT). This present research makes in attention the synthesis of an organic inorganic hybrid compound with new tetranuclear anionic bromobismuthates with formula: [C 12 H 20 N 2 ] 2 Bi 4 Br 16 •2H 2 O by slow evaporation at room temperature. It is characterized by X-ray diffraction. Indeed, this compound crystallizes in the monoclinic space group; P2 1 /c with the following parameters: a = 12.3534(6), b = 24.0296(9), c = 17.8715(8) Å, β= 92.302(5)°, V = 5300.8(4) Å 3 and Z = 4. The crystal structure consists of discrete [Bi 4 Br 16 ] 4− cluster and two kinds of the 2-phenylethylpiperazinium cations. The crystal structure is stabilized through intermolecular N H…Br, C H…Br and N H…O hydrogen bonds and Br…Br interactions. The vibrational absorption bands were identified by infrared spectroscopy. Moreover, computational studies are also performed using DFT calculations at B3LYP/6311++ G (2df,2p) level of theory to understand the typical conformers of 2-phenylethylpiperazine and their proton affinities. Indeed, the molecular orbital calculations such as HOMO-LUMO and molecular electrostatic potential (MEP) surfaces have been calculated. Crystal structure analysis was supported with the Hirshfeld surface (HS) analysis and fingerprint plots enabled the identification of the significant intermolecular interactions. The Hirshfeld surface analysis of intermolecular interactions confirmed that the contacts: Br…H/H…Br and H…H make the largest contribution to the HS and play a dominant role in the crystal structure of the investigated compound.

Synthesis, structural, spectral and antibacterial activity of organic-inorganic compound (C7H9N4O2).[ZnCl3(H2O)] with theophyllinium as Counter Cation

• The new organic-inorganic compound (C 7 H 9 N 4 O 2 ).[ZnCl 3 (H 2 O) was prepared and characterized. • The structure of the complex was determined by Single Crystal X-Ray Diffraction and confirmed by FTIR, 1 H RMN, UV-visible. • The antibacterial test was investigated with various pathogenic strains. Single crystals of organic-inorganic hybrid compound (C 7 H 9 N 4 O 2 ).[ZnCl 3 (H 2 O)] has been synthesized by slow evaporation at room temperature and characterized by X-ray diffraction analysis, UV-visible, infrared spectroscopy (FTIR), and 1 H NMR. The complex was crystallized in the monoclinic system with P 2 1 /c space group. Moreover, the composition of the complex contains a distorted tetrahedral [ZnCl 3 (H 2 O)] −1 anion and one protonated theophyllinium cation. The Zn(II) ion is coordinated by three Cl atoms and one oxygen atom from the water molecule in a close to tetrahedral geometry. The intermolecular hydrogen bonds (O–H…O, O–H…Cl and N-H…Cl) are together playing a vital role in stabilizing of the crystal packing. The antibacterial activity of the complex was evaluated against some bacteria Escherichia coli and Staphylococcus aureus . The compound shown greater antibacterial activity with a MIC value 1.25 mg/µL.

Four Dawson POM-based inorganic-organic supramolecular compounds for proton conduction, electrochemical and photocatalytic activity

Four new inorganic-organic hybrid compounds based on the Wells-Dawson polyoxometalate, namely. [Ni(H2bibb)2(H2O)3(α-P2W18O62)]·7H2O (1), [Co(H2bibb)2(H2O)3(α-P2W18O62)]·10H2O (2), [Cu(H2bibb)2(H2O)3(α-P2W18O62)]·10.5H2O (3) and [Zn(Hbibb)2(H2O)](α-P2W18O62)(H2bibb)·5H2O (4) (bibb ​= ​1,3-bis(1-imidazolyl)-5-(2-benzimidazolyl)benzene) have been synthesized by hydrothermal method. Compounds 1, 2 and 3 have similar configurations, of which the mononuclear units are all connected into a 2D supramolecular layer by hydrogen bonding and π … π stacking interactions, and then further extended into a 3D supramolecular structure. For compound 4, the binuclear {Zn2(Hbibb)4} units are connected to form a 3D supramolecular network through hydrogen bonding and π … π stacking interactions. Alternating-current impedance measurement suggests that the highest proton conductivity of compound 3 is up to 2.52 ​× ​10−4 ​S ​cm−1 (85 ​°C, 98% RH). The photocatalytic degradation of RhB by these compounds indicates that the dye degradation rate shown by catalyst 1 is the highest, reaching 67.14%. In addition, the electrochemical properties of these compounds are also investigated.

Methylhydrazinium lead iodide – one dimensional chain phase with excitonic absorption and large energy band gap

In this work the crystal structure of the new hybrid organic-inorganic compound has been studied using single-crystal X-ray diffraction (SCXRD). Methylhydrazinium lead iodide (MHyPbI3) crystallizes in monoclinic, centrosymmetric P21/c space group with a = 4.5067(4) Å, b = 19.1892(16) Å, c = 12.0029(12) Å and β = 98.178(8)°. The structure is built of edge-sharing [PbI6]4− octahedra forming parallel double chains along the [100] direction. MHy+ cations are placed between the chains. The motif is stabilized via two kinds of NH···I hydrogen bonds. RT absorption studies reveal the excitonic absorption band at 413 nm (3.00 eV). The estimated energy band gap value Eg is 3.11 eV (400 nm). At 367 K MHyPbI3 transforms to the new HT polymorph of P21/m symmetry with a = 8.895(1) Å, b = 18.185(1) Å and c = 13.197(1) Å and β = 99.10(1)°, that corresponds to the 2a monoclinic superstructure of the RT phase. The HT polymorph is metastable and returns to the pristine RT phase after ca. 50 min at room temperature.

Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials

Abstract Two photoluminescent copper(I) iodide inorganic-organic hybrid materials have been synthesized and structurally characterized as 1D-Cu2I2(bpoe)2 (1) and 1D-Cu2I2(bbtpe-m)2 (2) (bpoe = 1,2-bis(pyridin-3-yloxy)ethane, bbtpe-m = 1,1′-(3-methylpentane-1,5-diyl)bis(1H-benzo[1,2,3]triazole). Both are chain-like structures composed of Cu2I2 rhomboid dimers connected by bidentate ligands. Their emission colors range from cyan to yellow with relatively high internal quantum yields in the solid state. The tunable band gap and emission color is achieved by varying the LUMO energies of the ligands. The structures are robust and remain stable up to T = 260 °C, and coupled with their efficient and adjustable luminescence, facile synthesis, and non-toxic nature, these compounds demonstrate potential as rare earth element (REE)-free phosphors.