一类新型高荧光性类水滑石（Al-HTLc）的合成与性能

采用共沉淀法,合成、组装得到一类将铝离子（Al^3＋）量减少到一定值的镁铝型类水滑石,并使分散于其镁铝水滑石板层上的铝离子与板层间溶于亲油性阴离子中的计量8-羟基喹啉（8-HQ）配位,获得一类新型高荧光性类水滑石（Al-HTLc）．采用荧光光谱、红外光谱、紫外光谱、XRD、XPS和热分析等对其进行了表征．研究结果表明,该Al-HTLc在紫外光下可发出荧光强度高达4．9×10^5（a．u.）的强烈蓝绿色荧光（487nm）,荧光寿命为21．24ns,光量子产率为67％,高于纯8-羟基喹啉铝（Alq3）,且具有更高热稳定性,有望作为一类高性能的新型荧光材料而获得应用．     

水滑石无机阴离子交换剂的合成与表征

采用水热法制成了镁铝碳酸盐型、镁铝硝酸盐型、镁铝盐酸盐型、镁铝羟基型等插层镁铝类水滑石,比较了层间含不同阴离子类水滑石的结构差异和高温热处理后的结构稳定性.通过离子交换方式以镁铝羟基型为基材插层组装无机阴离子基团MoO42-、WO42-、CO32-和NO3-制得不同的阴离子插层类水滑石.通过XRD、TEM、XPS和热分析方法对镁铝类水滑石和阴离子插层类水滑石进行了表征.     

一种新型黄色荧光类水滑石材料的制备及表征

用适量的Zn(Ⅱ)取代镁铝水滑石中的Mg(Ⅱ),同时将一定量的2-对联苯基-8-羟基喹啉分散到类水滑石层间的亲油性阴离子中,使其与层板表面上的Zn(Ⅱ)配位,用一步法合成、组装得到一类新型黄色荧光类水滑石复合物(Zn-(HQ-4-biPh)-HTlc)。采用荧光光谱、红外光谱、X射线衍射、扫描电子显微镜和热分析等对其进行了表征。研究结果表明,Zn-(HQ-4-biPh)-HTlc在蓝光(481 nm)激发下可发出黄色荧光(554 nm),与其相应的含锌配合物(Zn[2-(p-biph)-8-Q-O]2)相比,不仅可节省配体用量,而且具有更高的发光强度和更好的热稳定性,有望在白光LED等光电领域得到应用。     

超分子结构草甘膦插层水滑石的组装及结构研究

提出了一种新的绿色农药缓释剂模型——超分子结构草甘膦缓释剂.依据插层组装理论,以阴离子层状材料镁铝水滑石(MgAl-LDH)为插层主体,以除草剂草甘膦为插层客体,由共沉淀法一步组装得到超分子结构草甘膦插层镁铝水滑石(MgAl-LDH-gly).通过对MgAl-LDH-gly的结构、主客体相互作用及化学组成确认,建立了MgAl-LDH-gly的近似超分子结构模型,并对其缓慢释放草甘膦的可行性进行了分析.     

超分子结构水杨酸根插层水滑石的组装及结构与性能研究

以锌铝水滑石ZnAl-CO3 LDHs为前体（主体），以乙二醇为分散介质，用离子 交换法组装了水杨酸根（客体）插层水滑石ZnAl-[o-HO(C6H4)COO]LDHs，并用XRD ，FT-IR，TG-DTA等手段对样品进行了表征。结果表明，能过控制离子交换条件， 水杨酸根阴离子可取代锌铝水滑石前体层间的CO3^2-离子，组装得到晶体结构良好 的水杨酸根插层水滑石。通过研究发现，主体水滑石层板与客体以静电力和氢键相 互作用，得到的超分子结构材料紫外阻隔作用增强并具有较好的稳定性，从而成为 一种集屏蔽和吸收双重功能的新型无机-有机得合紫外阻隔材料。     

超分子结构姜黄素插层镁铝水滑石的组装、结构及缓释性能

以镁铝水滑石为主体, 以中药提取物姜黄素为客体, 由共沉淀法、离子交换法和焙烧复原法三种不同方法组装得到超分子结构复合材料——姜黄素插层镁铝水滑石. 并用XRD, IR, HPLC等手段对该材料进行了表征. 结果表明, 共沉淀法和离子交换法成功组装得到两种不同结构的姜黄素插层产物, 使材料的层间距扩大为0.82～1.36 nm, 层间客体姜黄素阴离子是以平行或者单层垂直的定位方向排列于层间的. 考察了该材料在不同pH值的磷酸盐缓冲溶液中的缓释性能, 其缓释历程为客体阴离子与介质中 的离子交换过程. 该研究指出了阴离子层状材料——水滑石在中药释释剂领域的应用潜力.     

镍镁铝类水滑石的超分子结构、电子性质及稳定性

以Ni²⁺同晶取代Mg²⁺的方式构建镍镁铝类水滑石(HT)的周期性计算模型, 通过进行密度泛函理论计算,研究了含镍水滑石的的超分子结构、电子性质及稳定性. 结果表明, 随着镍离子逐渐取代镁离子, 金属离子之间的平均距离逐渐减小, 层间距逐渐增大, 与实验结果一致. 与此同时, 电子逐渐从主体层板向客体阴离子传递,导致主客体之间的静电作用力及整体超分子作用力逐渐增强, 结合能的绝对值逐渐增大, 体系的稳定性增加.在微观结构上, 电子传递行为使层板中平均金属―氧键键长逐渐减小, 且金属配位角的畸变情况得到一定程度的缓解, 这些变化都有利于形成更稳定的体系, 说明镍铝类水滑石在理论上比镁铝水滑石更稳定.     

酸性橙插层锌铝水滑石的组装及其结构与性能

采用共沉淀法合成酸性橙阴离子插层锌铝水滑石(Zn/Al-AO7 LDHs),研究不同pH值及原料金属离子配比对产物结构的影响,利用X射线粉末衍射(XRD),热分析(TG-DTA),傅里叶变换红外(FT-IR)等表征手段,对插层产物的结构进行表征,确定了制备酸性橙插层锌铝水滑石的最适宜条件.用量子化学的B3PW91/6-31G(d,p)方法对Zn/Al-AO7 LDHs模型分子的空间几何构型进行了优化,通过结构组合得到的层间距为2.33 nm,接近XRD测试得到的层间距,从而说明了酸性橙离子在水滑石层板间的排列方式.进一步以甲酰胺为溶剂对水滑石层板进行剥离,得到澄清溶液,根据剥离产物的XRD谱可以确定剥离实验成功.     

锌铝类水滑石的复原及表征(英)

本文采用焙烧复原法，在70 ℃以80%的乙醇溶液为分散介质，有机酸阴离子与煅烧后的锌铝类水滑石的物质的量之比为1∶9的条件下，实现了苯甲酸及苯二甲酸异构阴离子与锌铝类水滑石的插层反应，同时，还进行了等物质的量的两种酸与锌铝类水滑石（1∶1∶9）的插层反应。利用XRD和IR测试技术对样品结构进行表征，UV及HPLC对有机酸的反应量进行定量，并采用Gaussian-98软件包中ab initio分子轨道法（HF/6-31G）计算了各有机酸阴离子的分子结构，分析了其结构与插层行为的关系，并理论结合实验给出了各有机酸阴离子在锌铝类水滑石层间可能的空间构型。研究结果表明，苯甲酸及苯二甲酸异构阴离子在插层过程中表现出选择性，其优先进入锌铝类水滑石层间的顺序是：对苯二甲酸>邻苯二甲酸>间苯二甲酸>苯甲酸，且锌铝类水滑石对对苯二甲酸表现出较高的选择性，是环境友好的分离方法。     

发红色荧光的类水滑石材料的制备及在LED中的应用

通过共沉淀法合成了发红色荧光的类水滑石材料,采用硅烷偶联剂对其进行了表面改性,并利用荧光光谱、红外光谱、X射线衍射(XRD)和扫描电子显微镜(SEM)等对其结构和性能进行了表征,探讨了表面改性对荧光类水滑石的影响.将改性荧光类水滑石与发射波长为384 nm的In Ga N芯片组合制成发光二极管,器件发出明亮的红光.研究结果表明,改性的发红色荧光的类水滑石是制作白光二极管可供选用的红色发光材料.     

Preparation and characterization of a novel strong-fluorescent hydrotalcite-like compound (Al-HTLc)

A novel strong-fluorescent hydrotalcite-like compound (Al-HTLc) was synthesized by coprecipitation. In the sample, the content of aluminum(III) in the layers was decreased to a proper value. The Al3 ions coordinated with 8-hydroxyquinolines (8-HQ) which were dispersed into the anions in the interlayer region. The sample was characterized by XRD, XPS, FT-IR, TG-DSC, UV-Vis, and fluorescence spec- troscopy; its composition and structure were also determined. The results indicate that the sample can emit fluorescence (487 nm) with a strong fluorescence intensity (4.9×105 (a.u.)). The fluorescent lifetime and fluorescence quantum yield of Al-HTLc were measured to be 21.24 ns and 67%, respectively, higher than those of pure 8-hydroxyquinoline aluminum (Alq3). The result of TG-DSC measurement clearly shows the enhanced thermal stability of Al-HTLc compared with that of MgAl-LDH and pure Alq3. Al-HTLc may be used as a novel luminescent functional material.     

Synthesis and characterization of a strong-fluorescent Eu-containing hydrotalcite-like compound

A novel strong-fluorescent Eu-containing hydrotalcite-like compound (Eu-HTlc) was synthesized using the coprecipitation method, in which aluminum(III) was partially substituted by Europium (III) in the hydrotalcite-like layers, and thenoyltrifluoroacetone, 1,10-phenanthroline were dispersed into the anions in the interlayer region. The sample was characterized by XRD, XPS, FT-IR, ICP, TG-DSC, TEM and fluorescence spectra, and its composition and structure were determined. The results indicated that the sample exhibited a characteristic red light (614 nm). The fluorescent lifetime and fluorescence quantum yield of Eu-HTlc were measured to be respectively 893 μs and 66.44%, higher than those of Eu(III)-thenoyltrifluoroacetone-1,10-phenanthroline complex [Eu(TTA)₃phen]. The result of TG-DSC measurement showed the enhanced thermal stability of Eu-HTlc compared with that of MgAl-LDHs and Eu(TTA)₃phen. With excellent photoluminescent property and thermal stability, low contents of rare earth ions and ligands, the Eu-HTlc may become one of the novel fluorescent materials with potential applications.     

A two‐dimensional coordination polymer containing a two‐dimensional zinc–carboxylate layer constructed from helical chains: poly[(μ4‐benzene‐1,2‐dicarboxylato)zinc(II)]

The title compound, [Zn(C₈H₄O₄)]_n, consists of one Zn^II cation and one benzene‐1,2‐dicarboxylate dianion (BDC²⁻) as the building unit. The Zn^II cation is four‐coordinated by four carboxylate O atoms from four dianionic BDC²⁻ ligands in a distorted tetrahedral geometry. The Zn^II cations are linked by the BDC²⁻ ligands to generate a structure featuring two‐dimensional zinc–carboxylate layers containing left‐ and right‐handed helical chains. The two‐dimensional layers are stacked along the a direction. The thermal stability of the title compound has been studied.     

含能配合物[Zn(DAT)6](ClO4)2(DAT＝1,5-二氨基四唑)的合成、晶体结构及性质

采用直接法合成了新型高氮含能配合物[Zn(DAT)₆](ClO₄)₂(DAT＝1,5-二氨基四唑), 并用元素分析、傅立叶变换红外光谱对其结构进行了表征. 利用缓慢蒸发溶剂法培养出其单晶, 采用X射线单晶衍射仪测定其晶体结构, 结果表明该晶体属于三方晶系, 空间群, a＝b＝1.18398(9) nm, c＝0.65700(10) nm, γ＝120°, V＝0.79760(15) nm³, Z＝1. 在目标配合物的最小不对称单元中有1个Zn^2＋, 6个DAT分子和2个. 来自6个DAT分子的6个N原子分别与中心Zn^2＋配位, 形成一个六配位、非中心对称的畸变八面体结构. 用差示扫描量热分析、热重-微分热重分析结合红外光谱研究了标题化合物的热分解机理以及分解反应动力学参数. 测定了标题配合物的感度性能, 结果表明标题配合物具有一定的摩擦感度.     

catena‐Poly[[[4‐bromo‐2‐(2‐pyridyl­methyl­imino­meth­yl)­phenol­ato]­zinc(II)]‐μ‐chloro]

The title complex, [Zn(C₁₃H₁₀BrN₂O)Cl]_n, is a chloride‐bridged polynuclear zinc(II) compound. Each Zn^II ion is five‐coordinated in a square‐pyramidal configuration, with one O and two N atoms of one Schiff base and one bridging Cl atom defining the basal plane, and another bridging Cl atom occupying the apical position. The novelty of the compound lies in the bridging by chlorine of two square‐pyramidal Zn atoms, so that the bridging atom is apical for one Zn ion and basal for the other. This structural arrangement has not been observed before. The linked moieties form polymeric zigzag chains running along the a axis.     

Syntheses,crystal structures,and some spectroscopic properties of zinc(II) complexes with N2O2 ligands derived from m-phenylenediamine and m-aminobenzylamine

The reaction of bis(salicylidene)-m-phenylenediamine with zinc(II) ion affords a 2?:?2 dinuclear zinc(II) complex formulated as [Zn₂(L¹)₂]. A similar 2?:?2 dinuclear zinc(II) complex, [Zn₂(L²)₂], can be obtained by reaction of bis(salicylidene)-m-aminobenzylamine with zinc(II) ion. These two dinuclear complexes slightly differ in their crystal structures, especially coordination environments around the zinc(II) centers, depending on the dissimilar flexibilities of the two ligands. The differences between the two complexes are reflected in their diffuse reflectance and photoluminescence behaviors.     

Anionic clay–Pt metal nanoparticle composite through intercalation of hexachloroplatinate in nickel zinc hydroxysalt

Nickel zinc hydroxysalt–Pt metal nanoparticle composite was prepared by intercalation of the anionic platinum complex, [PtCl₆]^2? in nickel zinc hydroxysalt through ion exchange reaction and subsequent reduction of the platinum complex by ethanol. Powder X-ray diffraction and microscopy studies indicate that the process of reduction of the platinum complex in the interlayer region of the anionic clay takes place topotactically without destroying the layers.     

(3,4)‐Connected Twofold Interpenetrated Network with Right‐ and Left‐Handed Helical Chains: Synthesis,Crystal Structure,and Luminescence Sensing

The zinc(II) coordination polymer Zn₂(L)₂(bix)₂ · 2H₂O ( 1 ) [H₂L = 4,4′‐methylenebis(oxy)dibenzoic acid, bix = 1,4‐bis(imidazole‐1‐yl‐methylene)‐benzene] was synthesized by hydrothermal reaction. The title compound was characterized by single‐crystal X‐ray diffraction analysis, IR spectroscopy, and elemental analysis. The crystal structure determination reveals that compound 1 displays a twofold interpenetrated 3D framework, in which the Zn atoms are connected by the H₂L ligands into interesting right and left‐handed helical chains. Topological analysis reveals that the title compound displays a (3,4)‐connected (6³) (6⁵ · 8) topology. The solid‐state luminescent spectra was studied. Furthermore, the dispersed solution of compound 1 in DMF exhibits strong fluorescent emission, which could be quenched by trace amount of nitrobenzene.     

Synthesis,Structure, Antibacterial and Spectroscopic Properties of a Zinc(II) Complex with the Ligand 4‐Heptanoyl‐pyrazol‐5‐one

The long‐chain ligand, 1‐phenyl‐3‐methyl‐4‐heptanoyl‐pyrazol‐5‐one (HL) and its zinc(II) complex ZnL₂ were synthesized. The structure and the properties of ZnL₂ were characterized by elemental analysis, IR spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The zinc ion is five‐coordinated in a square‐pyramidal environment by four oxygen atoms of the HL ligands in the equatorial plane and one water molecule in the axial position. The water molecule is directly bonded to Zn²⁺ and involved in intermolecular hydrogen bonding network. The complex and its corresponding ligand were screened in vitro against some strains of the human pathogenic bacteria. The metal complex exhibits higher antibacterial activity than its corresponding ligand. The complex exhibits purple effect emission as the result of fluorescence from the intraligand emission excited state.     

Both visual and ratiometric fluorescent sensor for Zn2+ based on spirobenzopyran platform

A ratiometric fluorescent Zn²⁺ chemosensor, SPQH, based on spirobenzopyran platform, was synthesized. In aqueous HEPES 7.4 buffer solution, upon chelation with Zn(II), SPQH demonstrates high selectivity and subnanomolar sensitivity for zinc ion with 36-fold enhancement in the NIR fluorescence output.