Syntheses and Characterizations of Two New Organic-inorganic Hybrids Based on Heteropolymolybdates and Piperidine Molecules

Two new organic-inorganic compounds [（CH2）5NH2]3[PMo12O40]·3[（CH2）NH] 1 and [（CH2）5NH2]6[P2Mo18O62]·5H2O 2 have been synthesized using conventional and hydrothermal methods, respectively, and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. X-ray analyses show that in these compounds heteropolymolybdates [PMo12O40]^3- and [P2Mo18O62]^6- are reserved their Keggin or Dawson structures and linked to piperidine through electrostatic and hydrogen-bonding interactions.

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.

Organic-inorganic Hybrids Towards the Preparation of Nanoporous Composite Thin Films for Microelectronic Application

Silicon containing materials have traditionally been used in microelectronic fabrication. Semiconductor devices often have one or more arrays of patterned interconnect levels that serve to electrically couple the individual circuit elements forming an integrated circuit. These interconnect levels are typically separated by an insulating or dielectric film. Previously, a silicon oxide film was the most commonly used material for such dielectric films having dielectric constants( k ) near 4 0. However, as the feature size is continuously scaling down, the relatively high k of such silicon oxide films became inadequate to provide efficient electrical insulation. As such, there has been an increasing market demand for materials with even lower dielectric constant for Interlayer Dielectric(ILD) applications, yet retaining thermal and mechanical integrity. We wish to report here our investigations on the preparation of ultra low k ILD materials using a sacrificial approach whereby organic groups are burnt out to generate low k porous ORMOSIL films. We have been able to prepare a variety of organically modified silicone resins leading to highly microporous thin films, exhibiting ultra low k from 1 80 to 2 87, and good to high modulus, 1 5 to 5 5 GPa. Structure property influences on porosity, dielectric constant and modulus will be discussed.

Synthesis and Characterization of Layered Perovskite-type Organic-inorganic Hybrids(CnH2n+1NH3)2(CH3NH3)m-1PbmI3m+1(n=5-10,m=1,2)

Layered organic-inorganic hybrids（CnH2n＋1NH3）2（CH3NH3）m-1PbmI3m＋1 containing monolayer（m=1） and bilayer（m=2） perovsikte were synthesized by reactions in solution.The influences of the reactant ratio,solvent,reaction temperature,and reaction time on the structures of the products were investigated.The structures and the properties of the hybrids were characterized using X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and ultraviolet and visible（UV） absorption spectroscopy.The XRD patterns and the SEM images demonstrate that the pure bilayer perovskite hybrids are obtained.The UV-vis spectra indicate that the number of the inorganic perovskite layer（m） has greater impact on the band gap than the number of the carbon atoms（n）.The band gap of bilayer hybrids（around 1.9 eV） is significantly less than that of monolayer hybrids（around 2.2 eV）.

Synthesis and Characterization of Layered Perovskite-type Organic-inorganic Hybrids (R-NH_3)_2(CH_3NH_3)Pb_2I_7

Layered organic-inorganic hybrids containing bilayer perovsikte （R-NH3）2（CH3NH3）Pb2I7 （where R=C12H25,C6H5C2H4） were synthesized by reactions in solution. The influences of the solvents and the reactant ratio on the structures of the products were investigated. The structures and the properties of the hybrids were characterized using X-ray diffraction （XRD） and ultraviolet and visible （UV） adsorption spectra. For comparing with the bilayer perovskite hybrids in structure and band gap magnitude, the hybrids containing monolayer perovskite （R-NH3）2PbI4 were also synthesized and characterized. The results demonstrate that the thickness of inorganic layer has obvious effect on the tunneling magnitude of the band gap but the organic part can be micro actuator of band gap.

A Novel Inorganic-organic Hybrid Borate with Unique One-dimensional Infinite Aluminium-oxygen Chains

A novel inorganic-organic hybrid borate,[Al2（fum）（H3BO3）（OH） 4]n·n（H3BO3） （1,H2fum = fumaric acid） ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis. Crystal data for compound 1： orthorhombic,space group Pnma,a = 14.108（3） ,b = 6.9412（14） ,c = 14.995（3）A,V = 1468.3（5）A^3,Z = 4,Mr = 359.72,Dc = 1.627 g/cm^3,μ = 0.254 mm^-1,F（000） = 736,the final R = 0.0492 and wR = 0.1650 with I 〉 2σ（I） . In compound 1,each Al^Ⅲ ion is coordinated by six oxygen atoms to adopt a distorted octahedral geometry. Both fumarate anion and the coordinated boric acid act as bidentate bridging ligands to link two neighboring Al^Ⅲ centers simultaneously. Each Al^Ⅲ ion is bridged by two μ2-hydroxyl ligands to construct an infinite wave-like [Al2（fum）（H3BO3）（OH） 4]n chain. These one-dimensional chains form hydrogen bonds with free boric acid molecules giving rise to a three-dimensional supramolecular network.

An ionic 2D inorganic-organic hybrid of tris[((1H-tetrazol-5-yl)methyl)morpholine] dodecatungstophosphate(Ⅴ) pentahydrate:Synthesis X-ray crystal structure and spectroscopic characterizations

A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]^+ cations andα-Keggin[(PO_4)W_(12)O_(36)]^(3-) polyoxoanion.The most remarkable structural feature of this hybrid can...

An Organic-inorganic Hybrid Assembly Based on Novel Arsenatomolybdate and Cu~Ⅰ-Organic Units

A novel organic-inorganic hybrid arsenatomolybdate based on infrequent[AsMoO(OH)]unit,[Cu ~I(phen)][AsMoO(OH)]·3HO(1,phen=1,10-phenanthroline),has been hydrothermally synthe-sized.This structure was determined by single-crystal X-ray diffraction analysis,and further characterized by elemental analysis,and IR and UV spectra.To the best of our knowledge,it is the first report of a novel arsenatomolybdate subunit[AsMoO(OH)].Photoluminescence of 1 is ascribed to???*emission of the aromatic rings derived from the phen ligand.

Synthesis and characterization of luminescent organic-inorganic hybrid nanocomposite from polyhedral oligomeric silsesquioxane

A novel polyhedral oligomeric silsesquioxane(POSS)-based organic-inorganic hybrid nanocomposite(EF-POSS) was prepared by Pt-catalyzed hydrosilylation reaction of octahydridosilsesquioxane(T_8H_8,POSS) with a luminescent substituted acetylene(2- ethynyl-7-(4-(4-methylstyryl)styryl)-9,9-dioctyl-9H-fluorene(EF)) in high yield.The hybrid nanocomposite was soluble in common solvents such as CH_2Cl_2,CHCl_3,THF and 1,4-dioxane.Its structure and property were characterized by FTIR, NMR,TGA,UV and PL,respectively.The results show that the hybrid nanocomposite with high thermal stability emits stable blue light as a result of photo excitation and possesses high photoluminescence quantum efficiency(φ_(FL)).

Supramolecular Structural Inorganic-organic Hybrid[(4-Bromoanilimiun)([18]crown-6)]3[PMo(12)O(40)]·CH3CN

A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title compound was determined through single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system with P21/n space group. The crystal data are a = 18.9529（4）, b = 26.4444（5）, c = 19.0985（4） A, β = 90.132（6）o, V = 9572.1（3） A^3, Z = 4, Dc= 2.203 g·cm^（–1）, μ = 14.956 mm^（–1）, F（000） = 6192, S = 1.098, the final R = 0.0859 and w R（I 〉 2σ（I）） = 0.2100. Supramolecular cations are constructed through strong N–H…O hydrogen bonding interaction between the six oxygen atoms of [18]crown-6 molecule and nitrogen atom of（4-bromoanilimiun） cation. Three kinds of different arranged supramolecular cations exist in the title compound, which are filled into the large space formed by [PMo（12）O40] polyoxoanions. Thermogravimentic differential thermal analysis revealed that hydrogen bonding interaction and intermolecular interaction play an important role in maintaining the stability of the title compound.

Hydrothermal Synthesis and Crystal Structure of Inorganic-organic Hybrid Compound [H_3NC_2H_4NH_2]VOPO_4

An inorganic-organic hybrid compound, [H_3NC_2H_4NH_2]VOPO_4 was synthesized by means of the hydrothermal method. It was crystallized in a monoclinic system, a space group P2_1/c, with the crystal cell parameters: a=0.92285(11) nm, b=0.72994(9) nm, c=0.98495(11) nm, β=101.280(3)°, V=0.65067(13) nm^3, M_r=223.02 g/mol, D_c=2.277 g/cm^3, Z=4, R=0.0315, ωR=0.0865, GOF=1.085. The VO_5N octahedra chains are corner-linked by PO_4 tetrahedra; the VO_5N octahedra are all trans-linked with V—O bonds being alternately short and long. The monoprotonated ethylenediamine was intercalated between the layers with one end coordinating to V and the other end as an H-bond donor interacting with a terminal O atom of PO_4 from a neighboring sheet. The elementary analysis, infrared spectrum characters and thermal stability were also given.

A New Inorganic-organic Hybrid Based on Biisoquinoline and Hexachloridostannate:Structure, Photoluminescence, Electrochemical Behavior and Theoretical Study

A new inorganic-organic hybrid constructed from biisoquinoline dication and tin halide, [（BIQBT）（Sn Cl6）]n（1, BIQBT = 1,4-bis（isoquinoline） butane）, has been synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in the monoclinic system, space group Cc with Mr = 644.82, a = 16.589（3）, b = 18.388（4）, c = 8.5532（17）A, β = 108.75（3）°, V = 2470.6（9） A3, Z = 4, Dc = 1.736 g/cm^3, F（000） = 1281, μ（Mo Kα） = 1.697 mm^–1, the final R = 0.0197 and wR = 0.0493 for 4614 observed reflections with I 〉 2（I）. 1 consists of BIQBT^2＋dications and mononuclear hexachloridostannate Sn Cl62- anion, and hydrogen bonds among them contribute to the formation of a 1-D chain. Strong fluorescence can be detected in 1, which was explained by theoretical calculation. Its electrochemical behavior was investigated, and the theoretical calculations reveal that the π···π stacking interaction is dominated for their structural stabilization.

Recent advances in atomic imaging of organic-inorganic hybrid perovskites

Three-dimensional organic-inorganic hybrid perovskites(OHPs)hold a great prospect for photovoltaic applications due to their outstanding electronic and optical properties.These fascinating properties of OHPs in combination with their scalable and low-cost production make OHPs promising candidates for next-generation optoelectronic devices.The ability to obtain atomistic insights into physicochemical properties of this class of materials is crucial for the future development of this field.Recent advances in various scanning probe microscopy techniques have demonstrated their extraordinary capability in real-space imaging and spectroscopic measurements of the structural and electronic properties of OHPs with atomic-precision.Moreover,these techniques can be combined with light illumination to probe the structural and optoelectronic properties of OHPs close to the real device operation conditions.The primary focus of this review is to summarize the recent progress in atomic-scale studies of OHPs towards a deep understanding of the phenomena discovered in OHPs and OHP-based optoelectronic devices.

Synthesis, Structure, and Photoluminescence Property of a Novel One-dimensional Inorganic-organic Hybrid Gallophosphate JGP-2

A novel one-dimensional inorganic-organic hybrid gallophosphate compound, Ga（2,2＇-bipy）（HPO4）. （H2PO4）（denoted JGP-2） was synthesized hydrothermally with 2,2＇-bipyridine as a ligand and characterized by X-ray powder diffraction （XRD）, elemental analysis, inductively coupled plasma（ICP）, TGA analysis, solid-state ^31p NMR, and luminescence spectra and structurally determined by single-crystal X-ray diffraction analysis. JGP-2 crystallized in the triclinic system, space group P^-1（No.2）, with a=0.7818（1） nm, b=0.8611 （2） nm, c=1.0908（2） nm, V=0.6727（2） nm^3 and Z=2 with R1=0.0223. The structure of JGP-2 was built up by alternate arrangement of GaO4N2 octahedra, and HPO4（or H2PO4） tetrahedra to form an infinite one-dimensional corner-sharing-corner（CSC） chain. Through P sites, the CSC chains link with an unusual edge-sharing dimmer, Ga2F4（H2O）2, giving rise to a 4,10-membered ring net layered structure of JGP-7. On excitation at 254 nm, JGP-2 can emit strong blue light at ,λmax=388 rim. JGP-7 presents a strong fluorescence emission band centered at 394 nm（λex=340 nm）, the emission energy of JGP-7 is red-shifted comoared with that of JGP-2.

The Inorganic-organic Hybrid Junction with n-ZnO Nanorods/p-polyfluorene Structure Grown with Low-temperature Aqueous Chemical Growth Method

The inorganic-organic hybrid junction was synthesized on ITO glass substrate, which was consisted of an n-type ZnO nanorods （NRs） grown by low-temperature aqueous chemical growth method and a p-type polyfluorene （PF） organic film fabricated by spin-coating. The experimental results indicate that densely and uniformly distributed ZnO nanorods are successfully grown on the PF layer. The thickness of the PF layer plays a dominant role for the current-voltage （I-V） characteristic of the ZnO NRs/PF inorganic-organic hybrid junction device, and a p-n junction with obviously rectifying behavior is achieved with optimal PF layer thickness. The photoluminescence （PL） spectrum covering the broad visible range was obtained from the n-ZnO nanorods/p-polyfluorene （PF） structure, which was originated from the combination of the PF-related blue emission and the ZnO-related deep level emission.

New Inorganic-organic Hybrid Compound Containing One Dimensional Keggin Polyoxometalate [SiW_(11)O_(39)Co]^(6-) Chains: Preparation, Characterization and Application in Chemically Bulk-modified Electrode

A new inorganic-organic hybrid compound based on polyoxometalate and organic ligand formulated as （H2bpp）3[SiWlIO39Co]-2H20（1）[bpp=l,3-bis（4-pyridyl）propane] was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR, TG, and cyclic voltammetry. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of interesting cobalt-monosubstituted POMs one dimensional chain together with protonated bpp ligands. Additionally, the polyoxoanions combined with the discrete organic substrates by hydrogen bond interactions to afford a supramolecular 3D network structure. The hybrid compound 1 was used as a bulk modifier to fabricate a three-dimensional chemically modified carbon paste electrode（1-CPE） by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE were studied in detail. The results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite or bromate in 1 mol/L 1-12SO4 aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the insolubility of compound 1 and the supramolecular interactions existed between 1D POM anion chains and organic ligand bpp, which is very important for practical applications in electrode modification.

Preparation and properties of a POSS-containing organic-inorganic hybrid crosslinked polymer

A novel POSS-containing organic-inorganic hybrid crosslinked polymer was prepared by hydrosilylation reaction of octahydridosilsesquioxane （TsHs） with 4,4＇-bis（4-altyloxybenzoyloxy）phenyl （diene A）. Its structure and property was characterized by FFIR, 29Si NMR, TGA and ellipsometer, respectively. The results show that the hybrid polymer possesses high thermal stability and low dielectric constant of 1.97 at optical frequencies.

Organic-inorganic Hybrid Materials Based on Piperidine Derivatives and Semi-conductive Metal Iodine

Reactions of piperidine derivatives 4-(aminomethyl)piperidine(4-AMPD) and 1-methylpiperidin-4-amine(1-MPDA) with semi-conductive metal iodine SbI3 and PbI2 in concentrated HI aqueous solution afforded two one-dimensional(1 D) chain compounds [(4-AMPD)SbI5]n(1), [(1-MPDA)SbI5]n(2) and a two-dimensional(2 D) single layered organicinorganic hybrid material [(1-MPDA)PbI4]n(3), which were confirmed by X-ray single-crystal diffraction, infrared(IR) spectroscopy and powder X-ray diffraction(PXRD). Simultaneously, compounds 1~3 exhibit strong emission peaks at 600 nm for 1 and 2 and 570 nm for 3, which were originated from their inorganic moieties.

Syntheses, Structures and Fluorescent Properties of Two 1D Chain Organic Amines and Metal Iodine Organic-inorganic Hybrid Compounds

Two bifunctional amines, 4-(2-aminoethyl)morpholine and histamine, were heated with PbI_2 and BiI_3 in concentrated HI aqueous solution to give one-dimensional(1D) organicinorganic hybrid compounds [(C_6H_(16)N_2O)PbI4]n(1) and [(C_(16)H_(20)N_(20))Bi_2I_(10)](2), respectively. In 1, the [PbI6] octahedra formed double chain anions through sharing-corner and-edge, and the protonated(C_6H_(16)N_2O)^(2+) cations were located at the vicinity of the double chains by hydrogen bonds. In 2, the [BiI_6] octahedra firstly formed dimeric [Bi_2I_(10)]^(4-) anion through sharing edge, and subsequently, the protonated histamine cations worked as bridge to link alternately with [Bi_2I_(10)]^(4-) anion by hydrogen bonds to form organic-inorganic hybrid 1D chains. In addition, compound 1 emitted a green light at the excitation wavelength of 400 nm and the maximum emission wavelength is at 503 nm.

A Potassium Organic-inorganic Hybrid Complex with Channels Hosting Decorated Poly-anion Chains

A potassium organic-inorganic hybrid complex {H2[K（PMo12O40）（CH3CN）3]- （dpdo）2（H2O）}n 1 （dpdo = 4,4＇-bipyridine-N,N＇-dioxide） with special channels for the chain-like assembly of decorated Keggin-type anions was synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group Cmcm with a = 20.5328（17）, b = 16.8877（14）, c = 16,1454（14） A, V = 5598.4（8） A^3, Z = 4, C26H29N7O45KMo12P, Mr= 2380.91, Dc = 2.825 g/cm^3,μ = 2.813 mm^-1, F（000） = 4528, the final R = 0.0324 and wR = 0.0880 for 2577 observed reflections with I 〉 2σ（I）. Compound 1 exhibits a 3D network structure with large channels hosting decorated poly-anion chains as guests.