锌(II)与bipyO2三核配合物的合成和气敏性

锌(ＩＩ)与2,2′ 联吡啶 1,1′ 二氧化物ｂｙｐｙＯ2形成的配合物主要有[Ｚｎ(ｂｉｐｙＯ2)3](ＣｌＯ4)·2Ｈ2Ｏ、[Ｚｎ(ｂｉｐｙＯ2)3](ＰｔＣｌ4)·2Ｈ2Ｏ和[Ｃｏ(ｂｉｐｙＯ2)2(ＮＣＳ)2]等。我们在ＤＭＦ溶剂中合成了锌(ＩＩ)与ｂｉｐｙＯ2形成的三核配合物,测定了它的组成及ＩＲ谱气敏特性,发现对氨气有很高的敏感性和选择性。用它制作的传感器具有灵敏度高、选择性好、能耗低和常温下工作的特点,在涉氨化工生产的自动控制和氨气泄漏报警方面有一定的应用前景。1　实验部分ｂｉｐｙＯ2按文献[1]制备,经重结晶得白色晶体。Ｃ10Ｈ8Ｎ…     

Synthesis,crystal structure,and luminescence properties of a novel europium(III) complex

A novel europium(III) complex, [Eu(C₇H₅O₂)₂(C₇H₆O₂)₂(C₁₂H₈N₂)₂Cl], was synthesized and characterized by elemental analysis and single-crystal X-ray determination. It crystallizes in the monoclinic system, space group Cc with a = 17.2814(16), b = 17.9421(17), c = 14.9971(14) Å, β = 101.6510(10)°, Z = 4, ρ _c = 1.508 g/cm³, μ = 1.496 mm^?1, the final R = 0.0516 and wR = 0.1267 for 6435 observed reflections with I > 2σ(I). Structural analysis shows that the Eu(III) atom is nine-coordinated by one chlorine atom, four N atoms of two 1,10-phenanthroline (Phen) ligands, and four O atoms from four carboxybenzene ligands, to form a distorted tricapped trigonal prism. The luminescence spectrum of the complex indicates that the intensity of the emission wavelength at 612 nm is strongest among all emission wavelengths and the second phen ligand shows an enhancement effect on the luminescence of the complex.     

Synthesis,structure, and photoluminescence properties of Zn(II) complexes with 2-styryl derivatives of 8-hydroxyquinoline

Novel Zn(II) complexes with 2-styryl-8-hydroxyquinoline were synthesized and characterized by ¹H, ¹⁹F, and ¹³C NMR spectroscopy and X-ray diffraction analysis. Photoluminescence properties of the ligands and complexes in solutions were studied. The effect of substituents in the quinoline and phenylethenyl fragments on spectral characteristics was discussed.     

Synthesis,crystal structure,and properties of a binuclear Zn(II) macroheterocyclic complex based on ferrocene-thiocarbazide ligand

A binuclear macroheterocyclic complex Zn₂(FcL)₂ based on ferrocene-thiocarbazide (FcL) was synthesized. X-ray diffraction analysis shows that it belongs to the monoclinic system P2(1)/n space group, with a = 1.35379(17) nm, b = 2.6026(3) nm, c = 1.8693(2) nm, β = 95.687(2)° and final R indices R = 0.0796 and Rw = 0.2119. Two Zn(II) ions and two FcL ligands form a 22-membered macroheterocycle, further extended to an infinite 1-D helical chain by intermolecular hydrogen bonding. Spectral properties of the title complex and electrochemical properties of the ligand FcL are also discussed.     

The synthesis, crystal structure and spectroscopic properties of luminescent Zn(II) complex

A luminescent Zn(II) complex 1, ZnL2Cl2.2H2O has been synthesized where L=2,2',2'-(1,3,5-benzenetriyltrimethylidyne) as a yellow crystal. Single crystal X-ray analysis of the compound 1 shows a distorted tetrahedral structure. The compound 1 crystallizes in monoclinic, space group C2/c with a = 20.3151(19), b = 8.7299(9), c = 24.626(2) angstroms, beta = 107.474(2) degrees , V = 4165.9(7) A3. At room temperature, the complex 1 exhibits an intense blue emission at 474 nm upon 380 nm excitation.     

A 2-D tetrazole-based Zn(II) coordination polymer: crystal structure,dielectric constant,and luminescence

A tetrazole-based Zn(II) coordination polymer, [Zn(TMPT)₂] _n (1) (TMPT?=?5-(4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)-2H-tetrazole), was synthesized by in situ reaction of 4-((1H-1,2,4-triazol-1-yl)methyl)benzonitrile, Zn(NO₃)_2?·?6H₂O, and NaN₃ under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Complex 1 contains π–π stacking interactions between tetrazole rings and phenyl rings of the 2-D ordered layered structural framework, which contribute to the dielectric response. In addition, 1 was demonstrated to display strong blue fluorescence emissions in the solid state at room temperature.     

Synthesis,crystal structure,and kinetics of thermal decomposition of the Zn(II) complex with vanillin

A complex [Zn(C₈H₇O₃)₂(H₂O)₂] (C₈H₈O₃ is vanillin) has been synthesized and characterized by IR, elemental analysis, and X-ray diffraction single-crystal analysis. The crystals are monoclinic, space group C2/c, a = 22.236(8) Å, b = 10.594(2) Å, c = 7.8190(16) Å, α = 89.90(3)°, β = 106.87(4)°, γ = 89.99(3)°, V = 1762.6(8) ų, Z = 4, F(000) = 832, S = 1.079, ρ _c = 1.521g cm^?3, R = 0.0221, R _w = 0.0604, μ = 1.433 mm^?1. The Zn²⁺ ion is six-coordinated with a distorted octahedron geometry. The complex forms a three-dimensional network through intermolecular hydrogen bonds. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal conditions by the TG and DTG methods. The kinetic equation can be expressed as dα/dt = Ae^?E/RT 2(1 ? α)[1 ? ln(1 ? α)]^1/2. The kinetic parameters (E, A), activation entropy ΔS ^≠, and activation free-energy ΔG ^≠ were also gained.     

Synthesis,crystal structure,and luminescence properties of a novel 2D cobalt(II) polymer with 1-naphthalene acetate

The coordination compound [Co(H₂O)₂(C₁₂H₉O₂)₂] _n (I) was prepared by the reaction of 1-naphthaleneacetic acid and cobalt(II) acetate in a basic medium and was fully characterized by X-ray diffraction, elemental analysis, FT-IR, TG, and luminescence spectra. In the complex, the six-coordinated Co(II) ions are linked into a two-dimensional infinite layer with hydrophobic exterior by 1-naphthaleneacetate anions. At room temperature solid complex I exhibits favorable fluorescent emission resulted from the intraligand electronic transfer.     

Synthesis,crystal structure and electronic properties of bis(N-2-bromophenyl-salicydenaminato)copper(II) complex

A new series of complexes of the type bis(N-substituted-salicydenaminato)copper(II) (1–9), have been synthesized and characterized by IR, UV–Vis and elemental analysis methods. The molecular structure of bis(N-2-bromophenyl-salicydenaminato)copper(II) (6), was determined using X-ray crystallography. There are two independent molecules in the structure. Each shows a neutral, mononuclear, four-coordinate, square-planar trans-Cu[N₂O₂] geometry and, in each, the Cu atom and the ligating atoms are coplanar. The chelating N–Cu–O angle is 91.39(11)° for molecule one and 91.20(11)° for molecule two, whereas the non-chelating N–Cu–O angles are 88.61(11) and 88.80(11)°, respectively. The trans-N–Cu–N and trans-O–Cu–O bond angles are 180°. The electronic absorption spectra of copper(II) complexes (1–9), indicate that the d–d band energy is dependent on the nature and position of substituent on phenyl ring of the salicyldenimine ligand. The UV–Vis spectra in various solvents were measured and a relationship between absorption spectra and dielectric constant of the solvents is reported.     

Synthesis, structure and luminescence properties of Cu(ii), Zn(ii) and Cd(ii) complexes with 4'-terphenylterpyridine

The complexes [M(tptpy)(2)](ClO(4))(2) (M = Zn(ii) (1), Cd(ii) (2), and Cu(ii) (3)); tptpy = 4'-[1,1':4',1']terphenyl-4'-yl-[2,2':6',2']terpyridine = 4'-terphenylterpyridine) have been synthesized, structurally characterized by X-ray crystallography and subjected to preliminary luminescence studies. In the crystalline state, all the metal ions have an N(6) coordination sphere of distorted octahedral geometry and the structures of the Zn(ii) and Cd(ii) complexes are isomorphous but differ from that of the Cu(ii) complex, which also differs from the other two in that it is non-emissive. The structure determinations show that aromatic-aromatic interactions involving both the terpyridine heads and the terphenyl tails are important factors influencing the crystalline array. The emission spectra of the Zn(ii) and Cd(ii) complexes are very similar and show a considerable red-shift of the emission maximum compared to that of the free ligand.     

Preparation,thermal decomposition,and crystal structure of Zn(II) 2-chlorobenzoate complex with nicotinamide

A new Zn(II) 2-chlorobenzoate complex, [Zn(2-ClC₆H₄COO)₂(nad)₂] (nad = nicotinamide), was synthesized and characterized by elemental analysis, infrared (IR) spectroscopy, mass spectrometry, thermal analysis, and X-ray structure determination. The mechanism of thermal decomposition of the complex was studied by TG/DTG, DTA, IR spectroscopy, and mass spectrometry. The thermal decomposition is characterized as a two-step process. Zinc oxide was found as the final product of the thermal decomposition performed up to 900°C. Mass spectrometry was used to determine the volatiles released during thermal decomposition. The IR spectrum indicates that carboxylate is coordinated to zinc in monodentate coordination. [Zn(2-ClC₆H₄COO)₂(nad)₂] crystallizes in the monoclinic system, space group Pn, a = 10.376(2) Å, b = 10.100(1) Å, c = 12.604(1) Å, β = 100.79(1)°. The zinc is tetrahedrally coordinated by two nitrogens of nicotinamide and two oxygens of 2-chlorobenzoate.     

Synthesis,structure and magnetic properties of an iron(II) complex with nitronyl nitroxides

An iron(II) complex with nitronyl nitroxides, [Fe^II(dppNN)₂](BF₄)₂ · CH₃COCH₃ (1) (dppNN = 2,6-di(pyrazol-1-yl)-4-(4,4,5,5-tetramethyl-1-oxido-3-ylooxy-4,5-dihydro-3H-imidazol-2′-yl)pyridine) was synthesized. In 1 the central iron(II) ion was coordinated by two tridentate ligands with nitronyl nitroxides. Magnetic susceptibility measurements showed that χ_mT values below 130 K was almost temperature independent, while upon increasing temperature χ_mT values showed gradual increase, suggesting an occurrence of a spin transition from low to high spin state. Green light irradiation on powder sample at 5 K resulted in spin conversion (LIESST).     

Synthesis, structure and photophysical properties of a flavin-based platinum(II) complex

We synthesized a thiosemicarbazone-functionalized flavin (Fl-(H)TSC: 2-[2-(3,4-dihydro-7,8-dimethyl-2,4-dioxobenzo[g]pteridin-10(2H)-yl)ethylidene]-hydrazinecarbothioamide) and its Pt(II) complex [Pt(Fl-TSC)(2)], and characterized it using X-ray diffraction, UV-visible absorption and luminescence spectroscopy. X-ray structural analysis for [Pt(Fl-TSC)(2)] revealed that the structure of the isoalloxazine part was almost the same as that in lumiflavin (7,8,10-trimethylisoalloxazine), and the thiosemicarbazone moiety acted as a bidentate ligand to form a PtS(2)N(2) planar conformation. UV-visible absorption and luminescence spectra of these compounds were very similar to those of riboflavin, but the emission intensity and the lifetime decreased considerably. Theoretical calculations suggested that the charge-separated state (Fl˙(-)-TSC˙(+)) contributed to the faster quenching from the (1)π-π* emission state.     

Copper(II) trinuclear complex with trimesic acid salicylidene hydrazone: Synthesis,structure, and magnetic properties

A trinuclear copper(II) complex of trimesic acid salicylidene hydrazone (H₆L) having the composition [Cu₃L · 4Py] · CH₃OH was synthesized and characterized. By X-ray crystallography, the crystals are triclinic: a = 11.7940(4) Å, b = 13.7241(5) Å, c = 15.8993(6) Å, α = 107.4120(10)°, β = 94.2900(10)°, γ = 105.5650(10)°, space group \(P\bar 1\), Z = 2. The number of symmetrically unique reflections having I > 2σ(I) is 7636, R = 0.0465, and R _w = 0.1198. The newly prepared complex contains, in its unit cell, two [Cu₃L · 4Py] molecules which are linked to form a dimer on account of phenoxo bridges (the Cu-O bond length is 2.555 the Cu…Cu distance is 3.348 Separations between them are 9.414, 9.371, and 9.667 of temperature is satisfactorily fitted in terms of a triangular cluster model (?2J = 2.2 cm^?1) with extra intermolecular interactions (zJ′ = 0.4 cm^?1). EPR spectra of solutions at 360–380 K feature a poorly resolved HFS, whose modeling gives a satisfactory result with allowance for the interaction of unpaired electrons with three equivalent copper nuclei (g = 2.098; a _Cu = 25.8 × 10^?4 cm^?1).     

Synthesis and crystal structure of cadmium(II) complex with 2-pyrimidinecarboxamide

The complex [Cd(N₂H₃C₅ONH₂)₂(CH₃COO)₂] (I) was synthesized and its structure was determined. The crystals are monoclinic: space group C2/c, a = 14/416(1), b = 9.410(1), c = 13.708(1) Å, β = 113.82(1)°, V = 1701.0(1) ų, ρ(calcd.) = 1.862 g/cm³, Z = 4. The structure consists of individual complexes I united by the N-H…O hydrogen bonding system into supramolecular framework. The coordination sphere of the cadmium atom (on axis 2) involves two chelate pyrimidinecarboxamide ligands, which form five-membered chelate rings CdOCCN(Cd-N(2) 2.432(4), Cd-O(3) 2.388(4) Å), and two monodentate CH₃COO^? ions (Cd-O(1) 2.280(3) Å). The second O atom of the acetate group is involved in a weak contact with the Cd²⁺ ion (Cd-O 2.670(4) Å). With account for the latter two contacts, the coordination polyhedron of Cd is irregular octahedron.     

Synthesis,structure and luminescent properties of Cd(II) and Zn(II) complexes constructed from 3,5-dimethyl-2, 6-pyrazinedicarboxylic acid

[Cd₂(phen)₂(DPZDA)₂(H₂O)₂] · 8H₂O (1) and [Zn(phen)(DPZDA)(H₂O)] · 2H₂O (2) have been synthesized by reaction of Cd(NO₃)₂/Zn(NO₃)₂ with phen and DPZDA (where phen = 1,10-phenanthroline, H₂DPZDA = 3,5-dimethyl-2,6-pyrazinedicarboxylic acid) in aqueous ethanol solution. Elemental analysis, IR spectra, thermal analyses and X-ray single crystal diffraction were carried out to determine the composition and crystal structure of 1 and 2. In 1, a 2D supramolecular network containing a novel metal-water decamer were formed by hydrogen bonds. In 2, a 2D supramolecular structure was constructed from hydrogen bonds and π·· · π interactions. Moreover, 1 and 2 displayed photoluminescent properties in the blue range at room temperature.     

Synthesis,spectral characterization,and luminescence properties of a cup-like ligand and its magnesium(II) complex

A new tripodal ligand, N,N′,N″-tri(salicylaldehyde)triaminotriethylamine (1) has been synthesized and characterized by elemental analysis, IR and UV spectroscopy, MS, and X-ray crystallography. X-ray diffraction analysis reveals that the three chains of the ligand form a cup-like structure. The ligand’s magnesium(II) complex has been synthesized and characterized by elemental analysis, conductivity, and IR and UV spectroscopy. The luminescence properties of the ligand and its magnesium(II) complex were investigated in DMF, CH₃OH, and CH₃CH₂OH solution and in the solid state at room temperature.     

Copper(II) complex with 2-(diphenylacetyl)indanedione-1,3: Synthesis and structure

A copper(II) complex with 2-(diphenylacetyl)indanedione-1,3 (HL) was synthesized. CuL₂·0.5C₄H₈O₂ crystals prepared from chloroform + 1,4-dioxane are triclinic, space group P \(\bar 1\), a = 15.0206(9) Å, b = 16.0132(9) Å, c = 16.8323(10) Å, α = 109.6850(10)°, β = 96.4390(10)°, γ = 97.7120(10)°, Z = 4. A unit cell contains two crystallographically independent centrosymmetric dinuclear complexes of the same structure. Each copper(II) atom is coordinated by bidentate cis-oriented deprotonated ligands L at the corners of the square. Bridging 1,4-dioxane molecules make the CN of each metal atom five.     

Synthesis and structure of complexes of Co(II) acetate and Zn(II) chloride with 2-aminobenzothiazole

Complexes of Co(II) acetate and Zn(II) chloride with 2-aminobenzothiazole were prepared, and their structures were studied by IR spectroscopy and single crystal X-ray diffraction. The complexes have the composition [Co(CH₃COO)₂(2-aminobenzothiazole)₂] and [Zncl₂(2-aminobenzothiazole)₂]. The coordination core has a distorted tetrahedral configuration. The metal ion coordinates two nitrogen atoms of the thiazole rings and two oxygen atoms of acetate ligands or two chloride ions.