Hydrothermal syntheses and crystal structures of two organic–inorganic hybrid molybdovanadates based on [V2Mo6(OH)2O24]4− and [VMo12O40]3− polyoxoanions

Two new organic–inorganic hybrid cobalt-molybdovanadates [Co(phen)₃]H₂[H₂V₂Mo₆O₂₆] · 7H₂O (1) and [Co(2,2′-bipy)₃][Na(H₂O)₇][VMo₁₂O₄₀] (2) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV, XPS spectroscopy, thermogravimetric (TG) analyses, and X-ray single crystal diffraction. The molecular structure of 1 consists of a [V₂Mo₆(OH)₂O₂₄]^4? polyoxoanion, a [Co(phen)₃]²⁺, two H⁺ and seven lattice water molecules. The structure of [V₂Mo₆(OH)₂O₂₄]^4? consists of six MoO₆ octahedra and two VO₄ tetrahedra; six MoO₆ octahedra are linked by edge-sharing oxygens forming a {Mo₆} ring, and two VO₄ tetrahedra cap opposite sides of the {Mo₆} ring. The molecular structural unit of 2 is constructed from a typical Keggin-type [VMo₁₂O₄₀]^3? polyoxoanion and a [Co(2,2′-bipy)₃]²⁺ cation and a Na⁺ countercation; Co²⁺ is coordinated by six nitrogens from three 2,2′-bipyridines forming a distorted octahedron.     

Synthesis and structural characterization of a new trimetallic thiocubane cluster

The trimetallic cluster W2CuAgS4(TDT)2(PPh3)2-CH2Cl2 (TDT= [S2(C6H3)CH3]2-) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)2]2-(1) with AgNO3,CuBr and PPh3.The structure contains a [W2CuAgS4]4+ distorted cubane-like core.Two types of metal-metal bonds exist in the core.One is W-W bond of which length is 0.2871(1) nm,the other is W-M' (M'=Cu or Ag) bonds,whose mean distance is 0.2980 nm.The details of synthesis,structure,IR,UV-Vis and 31P NMR spectra are reported.The crystallographic data are:space group F21/n,with 0=1.6987(4),6=1.7763(6),c=1.8918(5) nm,β=98.54(2)°,V=5.645(3) nm3,Z=4,and final R=0.043 for 6437 observed reflections.     

Synthesis and studies of new organic conductors based on ET and EDT-TTF with the [ZnBr4]2− anions

New layer organic conductors based on bis(ethylenedithio)tetrathiafulvalene (ET)₄ZnBr₄Solv (Solv stands for solvent) were synthesized in various halobenzenes as solvents (C₆H₅X, X = Cl, Br, F and C₆H₄Y₂, Y = Cl, Br), as well as based on ethylenedithiotetrathiafulvalene (EDT-TTF)₄MBr₄(1,1,2-C₂H₃Cl₃) (M = Zn, Mn) and (EDT-TTF)₉(ZnBr₄)₂. The crystal structure of (ET)₄ZnBr₄(C₆H₄Cl₂) at room temperature was established. It was found to be composed of alternating conducting layers with various structure of stacks formed of the ET radical cations. Their conductivity and ESR spectra were measured. The ET compounds obtained are organic metals up to the temperatures of 4.2, 72, 80, or 183 K (depending on the solvent: C₆H₄Cl₂, C₆H₅Cl, C₆H₅Br, or C₆H₅F, respectively); the replacement of the solvent with more bulky 1,2-dibromobenzene led to the formation of a semiconductor. The compounds (EDT-TTF)₄MBr₄(C₂H₃Cl₃) with M = Zn, Mn and (EDT-TTF)₉(ZnBr₄)₂ retain metallic character of conductivity up to the temperatures of 260, 280, and 210 K.     

pH-Controlled assembly of two polyoxometalate chains based on [α-GeW11O39]8− and Eu3+: syntheses,crystal structures,and properties

Utilizing reactions of [α-GeW₁₁O₃₉]^8? and Eu³⁺ under different pH conditions, two types of polymer chains, Cs₃K[Eu₄(H₂O)₁₈Ge₂W₂₂O₇₈]?·?16.5H₂O (1) and Cs₃K₂[Eu(H₂O)₂GeW₁₁O₃₉]?·?10H₂O (2), have been isolated and characterized by elemental analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. The Eu/[α-GeW₁₁O₃₉]^8? ratio is 1?:?1 in polyanion 2a and is an infrequent 2?:?1 in polyanion 1a. The Ln?:?POM ratio can be increased by controlling the reaction conditions. The solid photoluminescence spectra of 1 and 2 have been investigated at room temperature. The luminescence of 1 and 2 are distinctly different owing to their different Eu coordination geometries. UV spectra and electrochemical properties of 1 and 2 have been investigated. Compound 1 displays good electrocatalytic activity toward the reduction of nitrite.     

Synthesis,structural characterization,and properties of an entangled metal–organic framework based on a flexible dicarboxylate and a rigid N-donor

Self-assembly of manganese acetate with 1,3-bis(4-carboxy-phenoxy)propane (H₂bcp) and 1,2-bis(4-pyridyl)ethene (bpe) under solvothermal conditions yielded a polymer {[Mn₂(bcp)₂(bpe)(DMF)]} _n (1), which shows 2-D?→?3-D inclined interpenetration with polyrotaxane character. The magnetic behavior of 1 shows antiferromagnetic exchange between Mn magnetic centers.     

Synthesis,characterization and photocatalytic properties of Mg1−xZnxAl2O4 spinel nanoparticles

Mg_1−xZn_xAl₂O₄ spinel nanoparticles with x = 0, 0.05, 0.10, 0.15 and 0.20 were prepared via the chemical coprecipitation method. The obtained samples were characterised by thermal gravimetric and differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, UV–Vis diffuse reflection spectrum, transmission electron microscopy and ²⁷Al MAS-NMR spectroscopy. Mg_1−xZn_xAl₂O₄ spinel powders with the mean crystallite size of around 11 nm–14 nm were obtained. The crystallinity of the MgAl₂O₄ samples increases with the increase in the calcination temperature. At the same calcination temperature, higher amount of Zn²⁺ substitution leads to the higher level of crystallinity, but has no apparent influence on the mean crystallite size of the samples. The photocatalytic activity of the obtained Mg_1−xZn_xAl₂O₄ spinel nanoparticles was evaluated by monitoring the degradation of methylene blue under UV light. The degradation rates of methylene blue using the MgAl₂O₄ nanoparticles prepared at the calcination temperatures of 700 °C and 800 °C are much higher than those prepared at 900 °C and 1000 °C. The photocatalytic activities of the spinel powders with lower level of Zn²⁺ substitution such as Mg_0.95Zn_0.05Al₂O₄ are inferior to that of MgAl₂O₄. Results of ²⁷Al MAS-NMR spectroscopy analysis and the first principle total density of state calculations reveal that this is probably due to the substitutions of Zn²⁺ decreasing the degree of Al³⁺ ions inversion over the sites of tetrahedral and octahedral coordination. With the increase in the amounts of Zn²⁺ substitution, the effects of Zn²⁺ additions on the photocatalytic activities become gradually predominant, leading to the increases in the degradation rates. The methylene blue degraded by 99% within 4 h using the Mg_0.8Zn_0.2Al₂O₄ spinel powders.     

Synthesis and characterization of two new metal–organic frameworks with interpenetrated structures and luminescent properties

Two new metal–organic compounds, [Ag₂(HADC)₂(bimh)] (1) and [Cd(ADC)(bpp)]_n (2) [H₂ADC = 1,3-adamantanedicarboxylic acid, bimh = 1,6-bis(2-methyl-imidazole-1-yl)hexane, bpp = 1,3-bis(4-pyridyl)propane], have been synthesized and characterized. Compound 1 exhibits a discrete symmetric unit with 0D→2D interpenetrating structure. Compound 2 crystallizes in a chiral space group P212121 and presents a threefold interpenetrated 3D diamondoid network containing three helical chains. Thermal stability, X-ray powder diffraction, and luminescence for 1 and 2 are also measured and discussed.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

Synthesis and antiadrenergic properties of β-substituted alcohols based on 6-hydroxymethylpyridoxine

An approach to the synthesis of epoxides based on 6-hydroxymethylpyridoxine acetals was developed. The epoxides obtained were involved in the ring opening reactions by nitrogen-, oxygen-, and sulfur-containing nucleophiles. Cytotoxicity and antiadrenergic properties of some synthesized compounds were studied on the models in situ and in vivo.     

Synthesis,crystal structure and properties of tungstoantimonates with CuII or NiII sandwiched by two [ α -SbW9O33]9− or [ β -SbW9O33]9− subunits

Two sandwich-type tungstoantimonates K₄Na₂H₃[Na₂K(H₂O)₂{Cu(H₂O)}₃(α-SbW₉O₃₃)₂]?·?15H₂O (1) and Na₄H₄[{Ni(H₂O)₃}₂{W(OH)₂}₂{β-SbW₉O₃₃}₂]?·?23H₂O (2) were prepared from aqueous solution by different strategies. They were characterized by X-ray structure analysis, electrochemical analysis, EPR and IR spectroscopy. Both compounds are sandwich-like tungstoantimonates built from two B-[SbW₉O₃₃]^9? building blocks. The polyoxoanion of 1 consists of two trivacant B-α-[SbW₉O₃₃]^9? moieties linked by three Cu²⁺ ions leading to a Hervé-type sandwich framework. The polyoxoanion in 2 is composed of two isomeric B-β-[SbW₉O₃₃]^9? subunits joined together by two Ni²⁺ and two W⁶⁺ ions resulting in a Krebs-type sandwich structure.     

Synthesis,crystal structure and luminescent properties of two complexes containing [Au(CN)2] − building blocks

Two supramolecular complexes, {{Ni(H₂O)(phen)₂[Au(CN)₂]}[Au(CN)₂]?·?1.5H₂O} _n (1) (phen?=?1,10-phenanthroline) and [H₂teta][Au₂(CN)₄]?·?2H₂O (2) (teta?=?5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene) have been synthesized and structurally characterized. Complex 1 was a one-dimensional infinite chain constructed by [Au(CN)₂]^? building blocks. In complex 2, there are one cation, one anion, and two water molecules in the asymmetric unit. The two complexes are interconnected through a combination of aurophilic attractions and hydrogen bonds and formed into 3D supramolecular structures. The aqueous solutions of 1 and 2 display interesting luminescence at room temperature.     

Synthesis,structural study,thermal, optical properties and characterization of the new compound [C_6H_7N_2O_2]_3TeCl_5·2Cl

The new organic-inorganic compound, [C_6H_7N_2O_2]_3TeCl_5·2Cl was synthesized and its structure was determined at room temperature in the triclinic system (P~-1) with the following parameters: a = 10.5330(11) ?, b = 10.6663(11) ?, c = 15.9751(16)?, α = 82.090(2)°, β = 71.193(2)°, γ = 68.284(2)°and Z = 2. The final cycle of refinement led to R = 0.057 and Rw = 0.149. The crystal structure was stabilized by an extensive network of N--H···Cl and non-classical C--H···Cl hydrogen bonds between the cation and the anionic group. Several thermal analysis techniques such as thermogravimetric analysis, differential scanning calorimetric analysis and evolved gas analysis were used. We used isoconversional kinetics methods to determine the kinetics parameters. We observe that the decomposition of [C_6H_7N_2O_2]_3TeCl_5·2Cl entails the formation hydrochloric acid of nitroaniline as volatiles. The infrared spectra were recorded in the4000–400 cm~(-1)frequency region. The Raman spectra were recorded in the external region of the anionic sublattice vibration 50–1500 cm~(-1). The optical band gap was calculated from the UV-Vis absorbance spectra using classical Tauc relation which was found to be 3.12 and 3.67 eV.     

Hydrothermal syntheses and structural characterization of two organic–inorganic hybrid compounds based on Lindqvist polyanions

Two organic–inorganic hybrid polyoxometalates {[V₂W₄O₁₉{Cu(2,2′-bipy)₂}₂] · (4,4′-bipy)} _n (1) and [Co(2,2′-bipy)₃][W₆O₁₉] · H₂O (2) (2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), constructed by Lindqvist polyanions and transition metal coordination cations, have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, UV spectra, thermogravimetric (TG) analyses, X-ray photoelectron spectroscopy (XPS), and single- crystal X-ray diffraction. Compound 1 is a neutral molecule and consists of a di-V^V substituted Lindqvist-type polyanion [V₂W₄O₁₉]^4?, two supporting copper cations [Cu(2,2′-bipy)₂]²⁺ and one free 4,4′-bipy. Neutral molecules of 1 are extended to a 2-D grid-like network by π–π stacking interactions between pyridine groups. The molecular structure of 2 contains one [W₆O₁₉]^2? cluster polyanion and a [Co(2,2′-bipy)₃]²⁺. Inductively coupled plasma (ICP) analysis and XPS spectrum of 1 prove the presence of V^V. TG curves of 1 and 2 indicate two weight loss steps.     

Synthesis,crystal structures,and photoluminescence of two new zinc complexes based on 2,2′-thiodibenzoic acid

{[Zn₂(tdba)₂(phen)₂(H₂O)₂]?·?2H₂O?·?2DMF} _n (1) and [Zn(tdba)(bpy)] _n (2) (H₂tdba?=?2,2′-thiodibenzoic acid, phen?=?1,10-phenanthroline, bpy?=?2,2′-bipyridine, DMF?=?dimethylformamide) were hydrothermally synthesized, and characterized by single-crystal X-ray diffraction analysis, FT-IR, and elemental analysis. The obtained complexes exhibit different structures. Compound 1 is 0-D with tdba connecting two Zn ions in a μ ₁–η ¹/μ ₁–η ¹ coordination forming a dinuclear molecule. Each molecule is further connected with neighbors via hydrogen-bonding and π?···?π interactions. Compound 2 displays a 1-D structure in which Zn²⁺ centers are connected via tdba anions into 1-D chains propagating along the a-axis; these chains are further packed via π?···?π interactions. In addition, photoluminescence for 1 and 2 has been investigated.     

Synthesis and characterization of novel polyimides based on thiazole-containing diamine

A new kind of aromatic diamine monomer containing thiazole unit,2-amino-5-(4-aminophenyl)-thiazole (AAPT),was synthesized in three steps,starting from 4-nitroacetophenone.A novel thiazole-containing polyimide was prepared via the polycondensation of AAPT with 6FDA by one-step method.The resulting polyimide exhibits excellent solubility,film-forming capability and high thermal resistance.     

Synthesis and Absorption Properties of Calix[6]amides—based Polymers

Reacting calix[6]arene hexaesters with poly(ethyleneimine),a series of calix[6]amidesbased polymers were obtained for the first time.It is found that they show high absorption capacities towards soft cations comparing to hard cations,and the absorption abilities enhanced with the increasing of calixarene content,which may indicates the cavity of calixarene plays crucial role in absorption.Polymer 2c shows good selective absorption capability towards Ag^ among the tested cations.     

Synthesis and structure of a new halophosphate Sr3P3O10Cl with the flexible [P3O10]5− anions

A new halophosphate crystal Sr₃P₃O₁₀Cl was grown in molten chloride flux media. It crystallizes in the centrosymmetric orthorhombic space group Pnma (No. 62) with a = 10.617(2) Å, b = 10.736(2) Å, and c = 8.7354(17) Å. In the structure, the basic building unit is the [P₃O₁₀]⁵⁻ anion, which is consist of three PO₄ tetrahedra by sharing the corner oxygen atoms. The two Sr atoms and the Cl atom are linked to construct an infinite [Sr₃Cl]⁵⁺ chain. The [P₃O₁₀]⁵⁻ anions are interconnected with the [Sr₃Cl]⁵⁺ chains to form a three-dimensional frameworks. Additionally, the first-principle calculation was employed to obtain the band structures and densities of states.     

Synthesis and characterization of two new inorganic–organic hybrid cobalt molybdenum(V) phosphates

Two new inorganic–organic hybrid cobalt phosphomolybdates (Hdien)₂[Co(dien)]₂[Co(dien)(H₂O)]₂[CoMo₁₂O₂₄(HPO₄)₂(H₂PO₄)₂(PO₄)₄(OH)₆]?···?5H₂O (1) and (H₂dien)₂[Co(dien)]₂[Co(H₂O)₂]₂[CoMo₁₂O₂₄(HPO₄)₄(PO₄)₄(OH)₆]?···?7H₂O (2) (dien?=?diethylenetriamine), involving molybdenum in the V oxidation state and covalently bonded transition metal complexes, have been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) chain framework, in which dien molecules adopt two kinds of coordination modes. Compound 2 shows a two-dimensional (2D) layer framework with three types of unusual tunnels. To the best of our knowledge, it is the first time [Co(dien)] units are directly incorporated into 1D and 2D skeletons of reduced molybdenum phosphates. The electrochemical properties of the two compounds were studied via the method of bulk-modified carbon paste electrodes. Furthermore, the magnetic properties of compound 2 are reported.     

Synthesis,aggregation-induced emission and thermally activated delayed fluorescence properties of two new compounds based on phenylethene,carbazole and 9,9′,10,10′-tetraoxidethianthrene

In the text, two luminescent materials ECPPTT and ECDPTT, have been designed and synthesized by integrating tetraphenyl/triphenyl-ethene(TPE/TrPE), carbazole group and thianthrene-9,9,10,10-tetraoxide unit. ECPPTT and ECDPTT possess obvious AIE and TADF capabilities, and show good thermal stability in their thin film of 240 °C and 262 °C, respectively. Non-doped organic light emitting diodes(OLED) using ECPPTT and ECDPTT as emission layer are prepared and exhibit blue-green and green emission color with peaks at 494, 517 nm, respectively. The non-doped OLED based on ECPPTT provides good peak EL efficiencies of 3.437 cdA^-1 and 10090cdm^-2; while non-doped OLED fabricated with ECDPTT affords a maximum current efficiency and a maximum luminance of 2.478 cdA^-1 and 7561cdm^-2. These results have demonstrated the feasibility of combing AIE and TADF units to design new molecules.