二(2-苯基-8-羟基喹啉)锌及其衍生物的电子光谱性质的含时密度泛函理论研究

采用从头算(ab initio)和密度泛函理论(DFT B3LYP)方法。对二(2-苯基-8-羟基喹啉)锌(Zn(qPh)₂)及其衍生物的基态结构进行优化，同时用ab initio HF单激发组态相互作用(CIS)法在6-31G基组上优化其最低激发单重态几何结构，用含时密度泛函理论(TD-DFT/B3LYP)及6-31G基组计算吸收和发射光谱。计算表明，该类物质电子在基态与激发态间的跃迁，主要是电子云分布由定域化向离域化的转变。吸收及发射光谱的计算值与实验值基本符合。该类化合物的电子亲和能较大，都是优良的电子传输材料，改变中心金属原子对配合物光谱性质影响不大。而羟基氧被硫原子取代后，化合物的吸收光谱产生明显红移。     

Synthesis and structure of di(2-phenyl-8-quinolyl) diselenide and zinc bis[(2-phenyl-8-quinolyl)selenolate]

Di(2-phenyl-8-quinolyl) diselenide [2-(C₆H₅)C₉H₅NSe]₂ and zinc bis[(2-phenyl-9-quinolyl)selenolate], Zn [2-(C₆H₅)C₉H₅NSe]₂, have been synthesized. The molecular and crystal structure of the compounds were determined by X-ray structural analysis. The structures of the 2-phenyl-8-quinolylselenol ligand in the molecules of di(2-phenyl-8-quinolyl) diselenide and in the intracomplex compound of zinc are compared. The effect of the phenyl group in position 2 of the quinoline nucleus on the formation of the molecules and their packing in the crystal structure is discussed.     

Structural and photophysical studies on a linear trinuclear zinc complex of 2-[(2-hydroxyethylimino)methyl]quinolin-8-ol

A linear trinuclear zinc complex was obtained when after refluxing 8-hydroxyquinoline-2-carboxaldehyde and 2-aminoethanol (in a 1:1 molar ratio) until the formation of the H₂L ligand, a methanol solution of zinc acetate dihydrate was added. Reaction between Zn(OAc)₂·2H₂O and H₂L, both in 3:2 or 4:2 ratios, yielded Zn₃(HL)₂(OAc)₄. This latter could be crystallographically characterised, and rather surprisingly, the potentially tetradentate HL⁻ is only acting as an O,N-donor, while two phenolate and four acetate bridges hold together the three zinc ions. A study of the luminescence properties in methanol solution showed that the quantum yield of Zn₃(HL)₂(OAc)₄ (Φ_F = 0.07) is slightly higher than that of 8-hydroxyquinoline-2-carboxaldehyde (Φ_F = 0.06).     

Intradiffusion coefficients for perchlorate ions in zinc perchlorate and zinc chloride solutions at 25°C: Comparing transport properties of zinc chloride and zinc perchlorate systems

Intradiffusion coefficients for³⁶ClO ₄ ^– have been measured in solutions of zinc perchlorate of concentration 0.1 to 3 mol dm^–3 at 25°C by the diaphragm cell technique. In addition, intradiffusion coefficients for perchlorate ions in zinc chloride solutions have been measured over a concentration range at 25°C. The results confirm previous work on the effect of complexation on diffusion in zinc chloride solutions above a salt concentration of 0.1M. The present data, together with literature data for diffusion coefficients of the other species present in the zinc perchlorate electrolyte system, have enabled a simple analysis of the hydration around the zinc ions to be carried out. This indicates that the water diffusion data are consistent with the zinc ions having an effective hydration sphere of 11 (±2) water molecules. This is in keeping with values obtained for other simple divalent electrolytes using the same model. The model is extended here to allow analysis of water diffusion in zinc chloride solutions taking into account the presence of complexed chloro-zinc species. The experimental data are consistent with the effective hydration of the chloro-zinc complexes being independent of the number of chloride ligands and equal to 18±3 over a concentration range of 0 tol mol-dm^–3. This postulate is discussed in terms of its consequences on the water ligand dynamics for the complex equilibria.     

Solvent extraction of zinc with 5,7-dichloro-2-methyl-8-hydroxyquinoline into chloroform

The distribution equilibria of the zinc complex with 5,7-dichloro-2-methyl-8-hydroxyquinoline in the water-chloroform system have been studied at 25 degrees . The influence of pH, reagent and metal concentrations, and the presence of sodium perchlorate in the aqueous phase has been determined. From quantitative evaluation of the extraction equilibrium data, it has been deduced that the complex extracted is the simple 1:2 chelate, ZnR(2), although at ligand concentrations higher than 0.3M, the self-adduct complex seems to begin to form. The extraction constant of the ZnR(2) species, refined by means of the program Letagrop-Distribution, has the value log K(ex) = - 6.15 +/- 0.07.     

一种新型含三苯胺的喹啉衍生物及其金属配合物的合成与表征

A new 8-hydroxyquinoline derivative(5)was synthesized and characterized by ESI-MS,~1H NMR spectroscopy,elemental analysis and IR spectroscopy.The photophysical properties of compounds 5,6 and 7 were also deteminedby UV-vis and FL spectroscopy.The vibrational frequency of ligand 5 predicted by using B3LYP method is in goodagreement with experimentally determined values.The compositions of the corresponding copper(Ⅱ)and zinc(Ⅱ)complexes were confirmed to be Cu(C_(29)H_(21)N_2O)_2·H_2O(6)and Zn(C_(29)H_(21)N_2O)_2·H_2O(7)by elementary analysis,thermogravimetry analysis and IR spectroscopy.     

2-对联苯-8-羟基喹啉锌的合成及其应用于新型白光OLED

合成了一种全新的有机发光材料2-对联苯-8-羟基喹啉锌(Zn[2-(p-biPh)-8-Q-O]₂), 通过¹H NMR, UV-Vis等对配合物的结构进行表征. 利用该材料制备了新型白光有机电致发光器件(OLED), 其结构为: ITO/NPB (N,N'-双(1-萘基)-N,N'-二苯基-1,1'-二苯基-4,4'-二胺)/BCP (2,9-二甲基-4,7-二苯基-1,10-菲咯啉)/Zn[2-(p-biPh)-8-Q-O]₂/Al. 通过调节空穴阻挡层BCP的厚度, 实现了NPB(蓝光发射)和Zn[2-(p-biPh)-8-Q-O]₂(黄光发射)作为器件双发光层的有效复合, 并研究了其发光机理. 当BCP层的厚度为2.0 nm时, 获得了稳定的白色发光; 该器件在6 V电压下启亮, 20 V电压时最大发光亮度达到130 cd/m², 电流效率为0.224 cd/A.     

Synthesis,characterization, structures,and DFT study of zinc(II) complexes with tributylphosphine chalcogenides

Four new zinc(II) complexes of the type [ZnCl₂(n-Bu₃PE)₂] (E=O (1), S (2), Se (3), or Te (4)) have been synthesized from zinc(II) chloride and the ligands n-Bu₃PE giving yields of 56–88%. The adducts were characterized by multinuclear (³¹P, ¹³C, and ⁷⁷Se) NMR, conductivity, IR spectroscopy and by X-ray analyses. Zinc complexes 1–4 are compriseS of two ligands coordinated to the metal center in a distorted tetrahedral arrangement. The P=E bond lengths of 1.497(7) (E=O), 2.000(4) (E=S), and 2.178(2) Å (E=Se) in these complexes are slightly elongated compared to those in the free ligand. In addition, a DFT/B3LYP theoretical study on the geometry optimization of the title ligands and their zinc complexes has been carried out in order to support and complement the experimental data and to further investigate the nature of the chalcogenide-metal interaction. The results show good agreement between the experimental and theoretical data.     

The role of anhydrous zinc nitrate in the thermal decomposition of the zinc hydroxy nitrates Zn5(OH)8(NO3)2·2H2O and ZnOHNO3·H2O

The steps associated with the thermal decomposition of Zn₅(OH)₈(NO₃)₂·2H₂O and ZnOHNO₃·H₂O are re-examined. Previous reports have suggested that Zn₅(OH)₈(NO₃)₂·2H₂O decomposes to ZnO via two intermediates, Zn₅(OH)₈(NO₃)₂ and Zn₃(OH)₄(NO₃)₂ whereas ZnOHNO₃·H₂O has been reported to decompose to ZnO via a Zn₃(OH)₄(NO₃)₂ intermediate. In this study, we demonstrate using TG, mass spectral analysis of evolved gases and in situ variable temperature powder X-ray diffraction analysis that, in fact, in the decomposition of Zn₅(OH)₈(NO₃)₂·2H₂O an anhydrous zinc nitrate intermediate is also involved. We, additionally, show that the decomposition of ZnOHNO₃·H₂O to ZnO also involves the formation of an anhydrous zinc nitrate intermediate. The anhydrous zinc nitrate formed in both cases is poorly crystallised and this observation may explain why this phase could not be observed by PXRD analysis in the previous studies.     

Synthesis and luminescence of polymeric metal complexes based on 1,10-phenanthroline and 8-hydroxyquinoline

A ligand containing different coordination groups, 5-([1,10]phenanthroline-[4,5-f]imidazo-2-yl)-8-hydroxyquinoline (PhenI8Q) has been synthesized and two corresponding polymeric metal complexes Cu(II) (1) and Zn(II) (2) were prepared by coordination polymerization of the ligand with copper(II) and zinc(II) halides, respectively. The ligand was characterized by ¹H-NMR, ¹³C-NMR, and Fourier transform-infrared (FT-IR) and its corresponding polymeric metal complexes 1 and 2 were characterized by FT-IR, UV-Vis, elemental analysis, thermal gravimetric analysis, and conductivity measurements. The absorption spectra and luminescence of the ligand, 1, and 2 were investigated by UV-Vis and fluorescence spectroscopy at room temperature. Compared with the ligand, the fluorescence spectra of the polymeric metal complexes exhibit blue shifts in dimethyl sulfoxide (DMSO) solution and bathochromic shifts in the solid state. Complexes 1 and 2 emit blue light with emission maximum (λ _{f max}) at 449 and 431 nm in DMSO solution and at 485 and 484 nm in the solid state, respectively.     

Structural Relationships between the Hemiporphyrazine Macrocyclic Ligand and its Metal Complexes. II.: Planar Neutral Ligand,C26H16N8, and Four Isomorphous Metal Complexes, [M(C26H16N8)(H2O)], M=Mn(II), Co(II), Cu(II), Zn(II)

Crystal and molecular structures of the planar neutral ligand, C₂₆H₁₆N₈, and the four isomorphous five-coordinated metal complexes, [M(C₂₆H₁₆N₈)(H₂O)], M = Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH₂, C₂₆H₁₆N₈, belongs to the P 2₁/c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3) Ä, β=94.66(6)°. The metal complexes monohydrate Mhp-H₂O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8×19.3×23.7 ų. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH₂·H₂O) and the nickel complex [Nihp]⁵. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)Å. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H₂O), M(II)-N1 (imine), M(II)-N3 (pyridine) are: 2.19(1), 2.00(2), 2.27(2)Å respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)Å for the cobalt complex; 2.33(1), 1.92(3), 2.18(1)Å for the copper complex; 2.110(5), 1.964(6), 2.252(6)Å for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.     

8-羟基喹啉及其衍生物的锌配合物合成研究进展

简述了有机发光材料8-羟基喹啉金属螯合物的发展,综述了固相法和液相法合成8-羟基喹啉锌,例举了在喹啉环上的2、5和7号位引入供电子基团或大共轭基团的8-羟基喹啉衍生物的锌配合物性质,介绍了通过改变聚合度制备8-羟基喹啉衍生物的锌配合物方法,杂环和8-羟基喹啉共同做锌的配体合成新的发光材料的方法;最后对8-羟基喹啉和8-羟基喹啉衍生物的锌配合物的合成进行总结和展望。     

双核锌配位化合物[Zn(C15H8O7S)(DMSO)]2•H2O的合成和晶体结构及光致发光性能研究

以白杨素为先导化合物, 对其进行磺化, 磺化衍生物与锌络合, 在含水10%的二甲基亚砜(DMSO)溶液中重结晶, 得双核锌配位化合物[Zn(C₁₅H₈O₇S)(DMSO)]₂•H₂O. 采用IR, ¹H NMR, DSC-TGA, 元素分析和X射线单晶衍射法对标题化合物进行了表征和晶体结构测定. 标题化合物属正交晶系, 空间群Pbcn, Zn(II)的配位数为5, 配位原子均为氧原子, 每个五配位的锌都具有四方锥型的配位构型, 被2个配体5-羟基氧负离子-7-羟基黄酮-6-磺酸根的5-羟基氧负离子桥联, 形成了一个中心Zn₂O₂的菱形平面. 水溶性白杨素黄酮配体与Zn(II)通过氢键、π-π堆积和配位作用自组装形成了一个三维结构的超分子化合物. 差示扫描量热分析(DSC-TGA)结果表明,标题化合物配体骨架分解温度为518.26 ℃. 同时, 标题化合物固体具有较强的光致发光现象, 在λ_ex＝423 nm条件下可发出λ_em＝488 nm的黄色荧光, 并对其发光机制进行了探讨.     

Selective synthesis of ZIFs from zinc and nickel nitrate solution for photocatalytic H2O2 production

Hydrogen peroxide (H₂O₂) is one of the most promising, green, and effective oxidants that can be used in different applications. In this study, zeolitic imidazolate frameworks (ZIFs), consisting of organic ligands and metal sites, were selectively prepared from zinc or nickel nitrate solutions for use in photocatalytic H₂O₂ production. High concentrations of zinc nitrate solution provided more metal sites to coordinate with 2-methylimidazole, producing ZIF-8 with larger particle size, whereas low zinc nitrate concentrations resulted in more interconnected N–H⋯N hydrogen bonds, forming 2D-layered ZIF-L, with smaller particle size. Various concentrations of zinc and nickel nitrate solutions produced ZIFs that exhibited ZIF-8 or ZIF-L topology, with bandgap energies of 5.45 and 4.85 eV, respectively. These samples could serve as promising photocatalyst for the successful production of H₂O₂ under Xenon lamp irradiation.     

The synthesis and characterization of aluminum,gallium and zinc formamidinates

Reactions of the formamidinate ligand, RN(H)C(H)NR, L^H, (R = 2,6-diisopropylphenyl), with AlMe₃, AlMe₂Cl, GaMe₃ and ZnEt₂ were investigated to examine potential coordination modes of the ligand and the effect of hydrolysis on the products. Nine new complexes have been fully characterized by X-ray crystallography and other spectroscopic techniques and highlight the diverse coordination modes of the formamidinate ligand.     

Synthesis,crystal structure,and properties of a tetrairon cluster based on 2-methyl-8-hydroxyquinoline

The synthesis, structure, and magnetic properties of a tetrairon(III) complex [Fe₄(μ₂-O)₂Cl₄(L)₄]·0.5H₂O (1, L = 2-methyl-8-hydroxyquinoline), which was prepared under solvothermal conditions and characterized by IR spectra, elemental analysis, TG, and single-crystal X-ray crystal diffraction, are presented. Each Fe center adopts a distorted trigonal bipyramid geometry and is coordinated with three oxygen atoms, one nitrogen atom, and one chlorine atom. Each 2-methyl-8-hydroxyquinoline is coordinated to two Fe^III ions with μ₂-η²:η¹ coordination mode. The magnetic properties of the complex are dominated by antiferromagnetic exchange interactions.     

Synthesis and luminescent properties of polymeric metal complexes containing bis(8-hydroxyquinoline) group

A novel ligand: 4,4′-bis(8-hydroxyquinoline-5-propenyl)-biphenyl (B8QPB) (1), has been synthesized by Witting-Horner reaction, and the corresponding two polymeric metal complexes were also prepared by polynuclear of the ligand with aluminium (III) (2) and zinc (II) (3) halides, respectively. The structure of the ligand was characterized by ¹H NMR, FT-IR and elemental analysis techniques; polymeric metal complexes were characterized by FT-IR, UV-vis, elemental analysis techniques, conductivity measurements and gel permeation chromatography (GPC). The results indicate that the stoichiometry of polymeric metal complexes is [(C₃₄H₂₄O₂N₂)₁₁Al₁₂Cl₂₈] and [(C₃₄H₂₄O₂N₂)₃₂(ZnCl₂)₃₃]. B8QPB coordinated with metal ions to form polymers. The luminescence properties of the complexes 1-3 were investigated by UV-vis and fluorescence spectra at room temperature. The experimental results show that polymeric metal complexes 2 and 3 emit blue/green luminescence at 514 and 504 nm in the solid state and at 470 and 507 nm in DMSO solution. Thermal properties measurement and analysis show that they have good thermal stabilities.     

IR,NMR, XPS study of 1-(d-3-mercapto-2-methylpropionyl)-l-proline and its zinc complexes

Two Zn(II) complexes of captopril were prepared and characterized with different analytical methods: IR, NMR and XPS. Captopril is a molecule which has been proven to be very effective in reducing blood pressure. The ligand chelates via the OCO group to a zinc ion and via S and amidic oxygen atoms to another zinc ion when the ZnL complex is obtained. The sulphur atom and the amidic CO group are the only atoms involved in the coordination when the sodium—zinc complex, Na₂ZnL₂, is synthesized.     

Solvent extraction of cobalt(II), zinc(II) and europium(III) with 4-thiobenzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one (SBMPP)

Solvent extraction of⁶⁵zinc,⁶⁰cobalt and^152+154europium from aqueous buffers into benzene containing 4-thiobenzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one (SBMPP) has been investigated in detail (μ=0.1, T=26±1°C). The species extracted and the values of log K_ex, where K_ex refers to the extraction equilibrium, are ZnL₂ (−2.68) CoL₂(−3.08) and EuL₃(−7.08), where L is the anion of the ligand. The sulfur analog appears to be more effective than the parent ligand 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one in the extraction of zinc(II) and cobalt(II), whereas the reverse is true with europium(III).     

Synthesis and characterization of a zinc(II) complex of 1,3-bis(1-benzylbenzimidazol-2-yl)-2-oxopropane

A ligand 1,3-bis(1-benzylbenzimidazol-2-yl)-2-oxopropane (Bobb) and the zinc(II) complex, [Zn(Bobb)₂](picrate)₂ · 2DMF, were synthesized and characterized by elemental analyses, electrical conductivities, IR, and UV. The crystal structures of the ligand and the zinc complex have been determined by single crystal X-ray diffraction. The ligand displays a V-shaped configuration and the Zn(II) cation is six-coordinate by four nitrogens and two oxygens from Bobb. The N₄O₂ donor set is a distorted octahedron.