Organic Inorganic Hybrid Compound Research Articles

Metal ion-dependent structural phase transition and impact of Jahn-Teller effect in two organic-inorganic hybrid compounds

Two new molecule-based organic-inorganic hybrid compounds, (H2dabco)[M(H2O)6][SiF6]2 (dabco = 1,4-diazabicyclo [2.2.2] octane, M = Mn2+ & Cu2+), affected by the different metal ions and Jahn-Teller effect of Cu2+, exhibiting metal...

Copper- and manganese-based layered hybrid organic–inorganic compounds with polymorphic transitions as energy storage materials

The bis(dodecylammonium) tetrachlorocuprate(ii) and bis(dodecylammonium) tetrachloromanganate(ii) show promise for passively cooling electronics due to their excellent thermal properties, including low thermal hysteresis and good stability.

Hydrogen storage metal-organic frameworks: From design to synthesis

For many years, there has been great interest in metal-organic frameworks, or MOFs. MOFs are a family of crystalline hybrid organic-inorganic compounds made up of strong coordination interactions connecting metal molecules to organic ligands. Due to their vast specific surface area, structural diversity, and adjustable pore size and functionality, they are highly advantageous in a variety of applications, including hydrogen storage. As a result, MOFs have been thoroughly researched. This study examines the drawbacks of traditional hydrogen storage methods before concentrating on MOFs’ potential as a cutting-edge material to get around these issues. The work also illustrates the benefits of MOFs in enhancing hydrogen adsorption performance by examining the synthesis techniques, functionalization tuning strategies, and their use with metal nanoparticle composites. Simultaneously, the significance of fine-tuning the functionalization and optimizing the performance of MOFs is underscored, and their potential to foster hydrogen-based economic growth is anticipated.

Alkali Metal Organic-Inorganic Hybrid Compounds with Different Crystal Dimensions Show Phase-Transition, Dielectric, and SHG Properties Based on a Quasi-Spherical Amine (1S,4S)-2,5-Diazabicyclo[2.2.1]heptane.

Reactions of a chiral and quasi-spherical molecule [1S,4S-2,5-2.2.1-H2dabch]I2 (1) with alkali metal halide MX (M = Na, K, Cs; X = Cl, Br) at room temperature produced a series of organic-inorganic hybrid (OIH) materials [1S,4S-2,5-2.2.1-H2dabch]NaBr3 (2), [1S,4S-2,5-2.2.1-H2dabch]CsCl3·H2O (3) and [1S,4S-2,5-2.2.1-H2dabch]KBr3·H2O (4). The single-crystal X-ray diffraction analysis revealed that the organic-inorganic framework structures comprised of the templating ligand and alkali metal halides (NaBr, CsCl, KBr) displayed dimensions spanning from one-dimensional (1D) to three-dimensional (3D). Moreover, the results of both differential scanning calorimetry (DSC) and dielectric measurements demonstrated that compounds 1-4 displayed reversible, high-temperature phase transitions and noticeable dielectric anomalies. In addition, the temperature-dependent second harmonic generation (SHG) results revealed crystals 1 and 3 can switch from the SHG-ON to the SHG-OFF state, which was proved by the variable-temperature X-ray diffraction. This research aims to streamline the exploration of multifunctional second harmonic generation (SHG) and dielectric materials that have been synthesized using chiral ligands and alkali metals. This will provide researchers with enhanced opportunities to delve further into this specific research domain.

Antimony Bromide Organic-Inorganic Hybrid Compound with a Long-Chain Diamine Showing Switchable Phase Transition and Second-Harmonic Generation Properties.

Organic-inorganic hybrid metal halides have attracted significant attention in recent years due to their excellent optoelectronic properties and potential applications in solar cells. Herein, the organic-inorganic hybrid molecule [N,N-dimethyl-1,3-propanediamine]SbBr5 (1) was synthesized by reacting a long-chain organic diamine N,N-dimethyl-1,3-propanediamine with SbBr3 as a metal halide precursor in HBr aqueous solution. Compound 1 possesses a one-dimensional chainlike structure with the second-harmonic generation switch and two continuous phase transitions above room temperature. The band gap of compound 1 is about 2.62 eV, exhibiting a semiconductive property, which may have important implications for the development of new optoelectronic devices.

Crystal growth, morphological, mechanical, spectroscopic studies, optical properties, molecular docking, ADME/T, Hirshfeld surfaces analysis and theoretical calculations of hybrid organic-inorganic phosphate compound

Molecular organic–inorganic single crystals of 4-carboxyanilinium dihydrogenphosphate [4-CADP] have been grown by the slow evaporation technique. The crystal structure was re-investigated by single-crystal X ray diffraction (SCXRD) analysis without signifiant differences from the previous study. 3D Hirshfeld surface and 2D fingerprint plot studies were performed to understand the intermolecular interactions of the 4-CADP crystal in graphical representation. Functional groups identification was studied with FT–IR spectroscopy. High transparency and a wide band gap of 5.44 eV were observed with UV–Vis spectroscopy. Geometrical structure of the 4-CADP compound was performed using the Density Function Theory (DFT) method at the B3LYP/3-21G and PBEPBE/3-21G levels of theory, along with the HF/3-21G basis set. The equilibrium geometry, highest occupied molecular orbitals (HOMO), lowest unoccupied molecular orbitals (LUMO), and molecular electrostatic potential map (MEP) were also calculated and presented. MEP a visual representation of the chemically active sites and comparative reactivity of atoms. Results revealed OH⋯O and NH⋯O contacts have the largest impact the Hirshfeld surface. The mechanical properties of the 4-CADP crystal were studied experimentally Vicker’s microhardness technique, which revealed that the grown crystal belonged to the softer category. 4-CADP crystal void estimation reveals the mechanical strength and porosity of the material.Last, it was tried to compare the biological activities of the studied hybrid molecule against enzymes: the crystal structure of acetylcholinesterase (AChE) (PDB ID: 4M0E), the crystal structure of butyrylcholinesterase (BChE) (PDB ID: 5NN0), crystal structure of alpha-galactosidase (α-Gly) (PDB ID: 1T0O), crystal structure of human carbonic anhydrase I (hCA I) (PDB ID: 2CAB), and the crystal structure of human carbonic anhydrase II (hCA II) (PDB ID: 5AML). Afterwards, ADME/T analysis was performed to predict the effects of molecules on human metabolism.

Photo-active hybrid materials based on polyoxometalate anion and ethidium cation

We report the synthesis and photoluminescence (PL) properties of three compounds [C21H20N3]2[HPMo12O40] (1), [C21H20N3]3[PW12O40]∙4C3H7NO (2) and [C21H20N3]4[SiW12O40] (3) consisting of ethidium cation (3,8-diamino-5-ethyl-6-phenylphenanthridinium) and Keggin type polyoxometalates. Compounds 1, 2 and 3 have been characterized unambiguously by the single crystal X-ray diffraction studies. The binding studies of inorganic-organic hybrid compounds 1, 2 and 3 with CT-DNA (calf thymus DNA) have been carried out and monitored by UV–Vis- and emission-spectroscopy. The compounds 1 and 2 show fluorescence enhancement where as compound 3 with silicotungstate polyanion shows fluorescence quenching. The photoluminescence properties of three hybrid compounds arise due to the interaction of ethidium cation with DNA. We have demonstrated that the interaction between ethidium cation and CT-DNA is influenced by a particular type of polyoxometalate (POM) Keggin anion. The crystal structures show supramolecular interactions between the Keggin anion and ethidium cation. Compounds 1, 2 and 3 are further characterized by routine spectral analysis.

Syntheses characterization, and photocatalytic property of an organic-inorganic compound obtained by bromine salt and the β-Mo8O26 anion

According to the structure/property characteristics of polyacids, the design and synthesis of new inorganic organic hybrid materials based on POMs is of great significance for the rapid and effective removal of pollutants in wastewater. In addition, many researchers have synthesized a large number of POMs-based inorganic organic hybrid compounds with organic cations as templates. Based on the above background, in this article, a new supramolecular compound named o-[C20H18N2O4][Mo8O26]0.5.H2O was obtained through hydrothermal method by reacting 1, 2-bis[4-nitrile-pyridine)-N-methylene]phenyldibromide (L1) with (NH4)6Mo7O24.4H2O. The compound was characterized by IR, PXRD, and single crystal X-ray analysis. Single crystal X-ray analysis shows that the compound consists of a [β-Mo8O26] 2–, a dicarboxylic acid chelating ligand and a water molecule. This compound exhibits good catalytic activity towards MB. The degradation rate of MB by photocatalysis of compound 1 was 75.2% . The novelty of this work lies in the synthesis of a cyano-hydrolyzed ligand and the high efficiency of MB degradation of the compound.

Scintillation characteristics of antimony based organic–inorganic hybrid compounds with a zero-dimensional structure

Antimony based organic–inorganic hybrid compounds (Ph4P)2SbCl5 (Ph4P: tetraphenylphosphonium) and (DTA)2SbCl5 (DTA: dodecyltrimethylammonium) with a zero-dimensional structure were fabricated, and the optical and scintillation characteristics were evaluated. A broadband photoluminescence possibly due to self-trapped exciton (STE) emission appeared at 692 nm for (Ph4P)2SbCl5 and 630 nm for (DTA)2SbCl5 under 370 nm excitation light. The quantum yields were 98 % for (Ph4P)2SbCl5 and 97 % for (DTA)2SbCl5. Under X-ray, the broad emission peak was also detected at 670 nm for (Ph4P)2SbCl5 and at 615 nm for (DTA)2SbCl5. Furthermore, scintillation decay time constants were 4.9 μs for (Ph4P)2SbCl5 and 5.0 μs for (DTA)2SbCl5. Moreover, the scintillation light yield of (Ph4P)2SbCl5 was estimated to be about 12,000 photons/MeV, whereas the light of (DTA)2SbCl5 could not be determined. In addition, afterglow levels were 56 ppm for (Ph4P)2SbCl5 and 130 ppm for (DTA)2SbCl5.

The Effect of Cation Incorporation on the Elastic and Vibrational Properties of Mixed Lead Chloride Perovskite Single Crystals

In recent years, there have been intense studies on hybrid organic–inorganic compounds (HOIPs) due to their tunable and adaptable features. This present study reports the vibrational, structural, and elastic properties of mixed halide single crystals of MAxFA1-xPbCl3 at room temperature by introducing the FA cation at the A-site of the perovskite crystal structure. Powder X-ray diffraction analysis confirmed that its cubic crystal symmetry is similar to that of MAPbCl3 and FAPbCl3 with no secondary phases, indicating a successful synthesis of the MAxFA1-xPbCl3 mixed halide single crystals. Structural analysis confirmed that the FA substitution increases the lattice constant with increasing FA concentration. Raman spectroscopy provided insight into the vibrational modes, revealing the successful incorporation of the FA cation into the system. Brillouin spectroscopy was used to investigate the changes in the elastic properties induced via the FA substitution. A monotonic decrease in the sound velocity and the elastic constant suggests that the incorporation of large FA cations causes distortion within the inorganic framework, altering bond lengths and angles and ultimately resulting in decreased elastic constants. An analysis of the absorption coefficient revealed lower attenuation coefficients as the FA content increased, indicating reduced damping effects and internal friction. The current findings can facilitate the fundamental understanding of mixed lead chloride perovskite materials and pave the way for future investigations to exploit the unique properties of mixed halide perovskites for advanced optoelectronic applications.

Highlighting non-covalent interactions to molecular structure, electronic and vibrational spectra in a new hybrid organic-inorganic cobalt complex: synthesis, experimental and computational study

Abstract In this study, a novel hybrid organic-inorganic compound, 4-(ammoniummethyl)pyridinium tetracholoraobaltate(II) monohydrate, with non-centrosymmetric properties have been synthesized and characterized by several techniques of powder and single-crystal X-ray diffraction, infrared IR and UV–Visible spectroscopies, and calorimetric (DSC) and the thermogravimetric (TG) analysis. The crystallization of this hybrid compound was found in a monoclinic system with a P21 space group. Additionally, the optimized structures of cation, anion and compound by using hybrid B3LYP method with 6-311++G(d,p) and 6-31+G(d) basis sets shown good correlations with the experimental data and the complete vibrational assignments and force constants are reported for three species. The surface morphology and the micrographs were checked by the scanning electron microscopy (SEM). The UV–Visible absorption spectrum has been used to study the optical properties and the energy gap of our compound. Hirshfeld surface (HS) analysis associated matched up with 2D fingerprint plots were used to confirm the existence of intermolecular and non-covalent interactions in the compound and confirmed by several topological approaches: Quantum Theory of Atom-in-Molecules (QTAIM), reduced density gradient (RDG) and molecular electrostatic potential surface (MEP). The frontier molecular orbitals HOMO and LUMO have been investigated for chemical reactivity and kinetic stability.

Analysis of the Structure, Thermal, and Molecular Dynamics of Organic-Inorganic Hybrid Crystal at Phases IV, III, II, and I: [NH2(CH3)2]2CdBr4.

A comprehensive understanding of the physicochemical properties of organic-inorganic hybrids is essential for their solid-state lighting applications. Therefore, a single crystal of [NH2(CH3)2]2CdBr4 was grown; the crystal structure was monoclinic, and the phase transition temperatures for the four phases IV, III, II, and I were 383 K (TC1), 417 K (TC2), and 427 K (TC3). Furthermore, the chemical shifts caused by the local field around 1H, 13C, 14N, and 113Cd changed continuously with temperature, especially near TC1, indicating that the local environment changes with temperature. Owing to the large change in 113Cd chemical shifts, the coordination geometry of Br around Cd in the CdBr4 tetrahedra changes near TC1. Therefore, it is proposed that Br plays a significant role in the N-H···Br hydrogen bond. Finally, the spin-lattice relaxation time T1ρ, representing the energy transfer around the 1H and 13C atoms of the cation, changed significantly with temperature. The activation energies obtained from the T1ρ results were two times larger at high temperatures than at low temperatures. This study provides an understanding of the fundamental properties of organic-inorganic hybrid compounds to broaden their applications.

Synthesis, crystal structure, and dielectricity of a displacement-type organic-inorganic hybrid phase transition compound: (C4H9NH3)6[InCl6]Cl3

An In(III)-based organic-inorganic hybrid phase transition compound, (C4H9NH3)6[InCl6]Cl3 (1, C4H9NH3+ = isobutyl-ammonium cation) was synthesized. Differential scanning calorimetry (DSC) test reveals that 1 experiences a second-order phase transition at 193/199 K (Tc). Crystal structure analyses prove that the phase transition is associated with the displacement motion and structural distortion of isobutyl-ammonium cations. The temperature dependence of dielectric constant for 1 displays apparent step-like anomalies around the Tc, which makes it a potential dielectric response material. It is expected that this work will be beneficial to explore novel organic-inorganic hybrid compounds.

Synthesis, structure and canted antiferromagnetism of layered cobalt hydroxide sorbate

Layered hybrid organic–inorganic compounds of the transition metal hydroxides, in which part of the hydroxide ions are exchanged for organic ligands that act as spacers of the 2-dimensional inorganic layers, elicit new or enhanced properties. The interlayer ligands enable fine-tuning of the physicochemical properties of the metal hydroxide layers, including their magnetism. Specifically, within the Co(OH)2 family of transition ion hydroxides, this approach has been leveraged to stabilize antiferromagnetic and ferrimagnetic ground states for pillared and layered complexes, respectively. Here, we further investigate the effects of changing dimensionality, local Co coordination, and interlayer spacing on the magnetic ground state of brucite-like β-Co(OH) layered complexes. We report the hydrothermal synthesis of a new crystalline material, Co(OH)(sorb), where the inorganic layers are spaced by monotopic, doubly unsaturated sorbate ligands (sorb = [C6H7O2]−). The material was structurally characterized using powder X-ray and neutron diffraction measurements and the crystal structure was solved ab initio from powder diffraction data and refined using the Rietveld method. The magnetic susceptibility and magnetization measurements reveal canted antiferromagnetic ordering with TN = 41.7 K. This report augments our understanding of tuning magnetism through dimensionality in layered complexes and represents a step forward in the design of new 2D layered hybrid compounds.

Structure of the new iron(II) oxalate potassium salt K2Fe[(C2O4)2(H2O)2]·0.18H2O.

The discovery of a new FeII oxalate framework of composition K2Fe[(C2O4)2(H2O)2]·0.18H2O is reported. Its crystal structure was solved by means of single crystal and powder X-ray diffraction. The new organic-inorganic hybrid compound crystallizes in the orthorhombic space group Pca21 with unit-cell parameters: a = 12.0351 (4) Å, b = 15.1265 (5) Å, c = 10.5562 (4) Å. This crystal structure, containing eight chemical formula, consists of a succession of FeO4(H2O)2 octahedra and K+ cations growing along b direction. Magnetization measurements indicate that the title compound is paramagnetic over the investigated temperature range (2-300 K). Both magnetization and 57Fe Mössbauer data indicate that Fe2+ is in a high-spin state.

A new Cu-halide organic-inorganic hybrid compound's synthesis, single-crystal X-ray diffraction, vibrational investigations, optical characteristics, and DFT calculation: (C12H20N2)CuCl4

Through gradual evaporation at room temperature, single crystals of a novel Cu(II) halide complex (C12H20N2)CuCl4 (symbolized by 1PEPCu) were formed. Physical-chemical techniques such as X-ray diffraction, IR and Raman spectroscopy, UV–visible absorption, luminescence, and thermal analysis were used to identify this substance. CuCl42-anions and 1–2-phenylethylpiperazine-1,4-diium dications make up the crystal structure. Hydrogen bonds kept these components together, and van der Waals interactions also helped. To determine the relative significance of intermolecular interactions, Hirshfeld surfaces were used to explore the interactions between molecules. The presence of the vibrational functional groups of organic and inorganic substances is confirmed by the IR and Raman spectroscopy investigations. In addition, calculations using Density Functional Theory (DFT) have been carried out to precisely infer the experimental finding, and excellent agreement has been obtained. At room temperature, the UV–visible absorption and luminescence spectroscopies were investigated. The thermal behavior was investigated using TGA and DTA analyses. A molecular docking study suggests that 1PEPCu may have an inhibitory effect on coronavirus proteins (COVID-19 and SARS-CoV2).

Imatinib cation based MOIFs with [Fe(CN)5NO]2−, [Fe(CN)6]3− [Fe(CN)6]4− as adsorbent of organic pollutants, and their protein interaction study

Inorganic-organic hybrid (IOH) compounds are being widely used in the design of multifunctional materials owing to their rich properties and flexible assembly. Here, we report three metal organic ionic frameworks (MOIFs)/ IOH, for the adsorption of toxic organic pollutants and Bovine Serum Albumin (BSA) interaction, synthesized via simple ion-exchange mechanism in water using Na2[Fe(CN)5NO], K3[Fe(CN)6], K4[Fe(CN)6] and 4-[(4-methylpiperazin-1-yl)methyl]-N-(4-methyl-3-{[4-(pyridin-3-yl)pyrimidin-2yl]amino}phenyl) mesylate (ImM). These were characterized through powder XRD, NMR, UV/ Vis and FTIR techniques for their structural elucidation. The thermal gravimetric analysis (TGA) revealed their two transitions due to loss of water and organic compound. Additionally, the band gap was found in the range of 3.2 to 3.3 eV, inferred their applicability in the field of semiconductors. MOIFs have shown the adsorption of toxic pollutants (Organic dyes) investigated through thermal kinetics and activation parameters which inferred about the interaction between organic dyes and MOIFs as characteristics for the adsorption system. Adsorption has also been analyzed through conductivity data where according to Ostwald's dilution law for weak electrolytes was applied. For knowing medicinal aspects, MOIFs have also been tested for BSA binding activity analyzed with UV–Vis, fluorescence and docking studies, which showed good quenching efficacy as well as interaction ability.

Synthesis, crystal growth, electronic structures and optical properties of wide bandgap semiconductor (CH3NH3)2HgI4

The synthesis, crystal growth and electronic structures, as well as optical properties of Hg-based hybrid organic-inorganic compound (CH3NH3)2HgI4 are reported. Single crystal was grown through the anti-solvent method, yielding the faint yellow (CH3NH3)2HgI4 flake crystals. The structural analysis revealed that (CH3NH3)2HgI4 crystallized in the orthorhombic space group Pbca with a 0D crystal structure featuring anionic [HgI4]2- units that were surrounded by CH3NH3+ cations. Furthermore, (CH3NH3)2HgI4 does not decompose when being exposed to air, but the crystallinity slowly decays over time in air at room temperature. TGA and DSC show that it is stable for (CH3NH3)2HgI4 from room temperature to 223 °C. It shows that (CH3NH3)2HgI4 is a slightly indirect nature with 3.276 eV of band gap based on density functional theory calculations, which is close to 3.18 eV derived from UV–vis–NIR spectra of (CH3NH3)2HgI4 crystal. In addition, room temperature photoluminescence (PL) spectra of (CH3NH3)2HgI4 yields broad peaks at 540 nm with full width at half maximum (FWHM) values of 201 nm. These PL peaks are tentatively assigned to self-trapped excitons following the crystal and electronic structure considerations. The bands around the Fermi level have small dispersions, which is indicative of high charge localization with significant exciton binding energies in (CH3NH3)2HgI4. PL analysis indicates that (CH3NH3)2HgI4 may have potential research value as white-light-emitting phosphors and scintillator.

Physico-Chemical Characterization, DFT Modeling and Biological Activities of a New Zn (II) Complex Containing Melamine as a Template

Single crystals of a new organic–inorganic hybrid compound (C3H7N6)2[ZnCl4]·H2O was synthesized and characterized by X-ray diffraction at room temperature, FT-IR and FT-Raman spectroscopies, optical absorption and photoluminescence behavior. The title compound belongs to the triclinic space group P1¯, and in the crystal structure, the inorganic layers are built from tetrachloridozincate anions [ZnCl4]2− and free water molecules, linked together by O–H···Cl hydrogen bonds and halogen···halogen interactions. In addition, Hirshfeld surfaces and 2D fingerprint plots estimate the weak intermolecular interactions accountable for the generation of crystal packing. The optimized geometry, vibrational frequencies and various thermodynamic parameters of the title compound calculated using density functional theory (DFT) methods are in agreement with the experimental values. The theoretical calculations were performed using the DFT method at WB97XD/Lanl2dz basis set levels and we discussed topological analysis of atoms in molecules (AIM) at the BCP point. A detailed interpretation of the IR and Raman spectra were reported. Additionally, the simulated spectrum satisfactorily coincided with the experimental UV-Visible spectrum. A wide band gap exceeding 4 eV of the synthesized compound was recorded. The photoluminescence (PL) was characterized through two bands successively at 453 and 477 nm. Ultimately, antimicrobial activity and enzymatic inhibition assays of the complex were also investigated through microbial strains, agar diffusion method, minimum inhibitory concentration (MIC) determination, lipase and phospholipase A2 inhibition.

Synthesis, crystal structure, thermal, spectroscopic and dielectric properties of partial substituted hybrid compound: (C6H5NH3)2[Cd1.44Zn0.06Cl5

A novel partial substituted (C6H5NH3)2[Cd1.44Zn0.06Cl5] organic–inorganic hybrid compound was grown by slow evaporation method at room temperature and characterized by Infra-red spectroscopy and Raman scattering, single crystal X-ray diffraction (SC-XRD), room temperature RT-XRPD and variable temperature (VT-XRPD) X-ray powder temperature, thermal properties (TGA and DSC) and dielectric permittivity. SC-XRD illustrates that the studied material belongs to the centrosymmetric orthorhombic space group Pcab with the following cell parameters: a = 7.4013(16)Å, b = 19.290(4)Å, c = 24.402(5)Å, Z = 8. The atomic arrangement of the crystal structure is described as inorganic infinite layers between wich organic cations are intercalated. Its structure provided a new interesting example of infinite two-dimensional inorganic layers built up [Cd/Zn1.5Cl5]n-2n octahedral following the c→ crystallography direction. The crystal packing is governed by non-covalent interactions such as hydrogen bonds and Columbic interactions (cations-anions), forming a three dimensional supramolecular network. The intermolecular interactions were studied by Hirshfeld surface analysis and 2D fingerprint plots. RT-XRPD proves that the crystalline material is pure. Differential scanning calorimetry (DSC) analysis reveals that the studied material undergoes one phase transition of order–disorder type around 59 °C. VT-XRPD and dielectric measurements were performed in the aim to confirm and to discuss the mechanism of phase transition.