含8-羟基喹啉侧基聚酯及其锌和铝配合物的合成与荧光性质

经多步反应合成3种含8-羟基喹啉侧基聚酯(P7~P9),进一步与无水醋酸锌和六水氯化铝反应,得到6种聚酯锌、铝配合物(P7-Zn~P9-Zn,P7-Al~P9-Al)。 采用元素分析、红外光谱、紫外可见光谱、核磁共振氢谱、凝胶渗透色谱、热重分析仪、差示扫描量热和荧光光谱等技术手段对其结构和性能进行表征。 P7~P9易溶于N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜(DMSO)和N-甲基吡咯烷酮(NMP),P7-Zn~P9-Zn和P7-Al~P9-Al部分溶于DMF、DMAC、DMSO和NMP。 P7~P9的质均相对分子质量(M_w)为1.79×10⁴、2.14×10⁴和2.52×10⁴ g/mol,相对分子质量分布指数PDI为1.54、1.64和1.72。 P7~P9的5%失重温度分别为291.6、291.3和284.9 ℃,P7-Zn~P9-Zn、P7-Al~P9-Al的5%失重温度分别为348.7、339.2、334.6、316.1、316.7和316.0 ℃。 P7~P9的玻璃化转变温度(T_g)分别为121.8、106.2和86.4 ℃,聚酯锌、铝配合物的T_g均高于180 ℃。 P7~P9的DMF溶液(5×10^-5 mol/L)在413~418 nm处发紫色荧光,P7-Zn~P9-Zn、P7-Al~P9-Al的DMF溶液(5×10^-5 mol/L)分别在509~513和485~487 nm处发强绿色荧光,固体分别在516~519和492~497 nm处发强绿色荧光。 P7~P9、P7-Zn~P9-Zn和P7-Al~P9-Al的荧光量子产率分别为5.5%~8.4%、21%~28%和23%~29%。     

2-乙烯基氟代苯-8-羟基喹啉锌配合物的合成及光学性能研究

设计合成了2种新型的含不同氟原子数的8-羟基喹啉衍生物配体:(E)-2-[2-(2-氟代苯基)乙烯基]-8-羟基喹啉(4a)和(E)-2-[2-(五氟苯基)乙烯基]-8-羟基喹啉(4b)及其相应的锌配合物5a和5b,利用1H NMR、IR、MS、元素分析确认了产物结构。通过紫外滴定模拟了金属锌与配体4a和4b的配位过程,测定了其在二甲基甲酰胺(DMF)溶液中的荧光性质。荧光光谱显示:配体4a和4b在DMF溶液中的λmax分别为505 nm(蓝绿色)和517 nm(绿色),配合物5a和5b的λmax分别为559 nm(青绿色)和599 nm(黄色),配位后体系共轭程度增大,荧光光谱发生明显的红移。而且随着取代氟原子的增加,配体和配合物的荧光光谱也发生明显的红移。荧光光谱显示氟原子取代数量的改变可以调控8-羟基喹啉锌配合物的发光性质。     

2-乙烯基硝基苯-8-羟基喹啉锌配合物的合成及紫外、荧光性质研究

设计合成了3种8-羟基喹啉衍生物配体:(E)-2-[2-(2-硝基苯基)乙烯基]-8-羟基喹啉(4a),(E)-2-[2-(3-硝基苯基)乙烯基]-8-羟基喹啉(4b),(E)-2-[2-(4-硝基苯基)乙烯基]-8-羟基喹啉(4c)及其相应的锌配合物5a～5c,产物经1H NMR,IR,MS和元素分析技术进行了结构表征.通过紫外滴定模拟了金属锌与配体的配位过程,分别测定了它们固态和溶液状态下的荧光性质:光谱显示化合物5a～5c固体荧光光谱的λmax分别是596,625,592 nm,在DMF溶液中的λmax分别是562,536,618 nm.荧光光谱显示硝基位置的改变可以调控8-羟基喹啉锌配合物的发光性质.     

含噻二唑基硫脲类化合物的合成

以噻二唑-2-氨甲基酚(1)为原料, 与异硫氰酸苯酯反应, 以中等到良好的产率得到噻二唑基N-苯基取代硫脲类化合物(3a~3i); 而化合物1与活性较高的N,N-二甲胺基硫代甲酰氯反应, 则可以得到—NH和—OH同时反应的含有N,N-二甲基硫脲和N,N-二甲基硫代氨基甲酸芳酯官能团的产物. 利用核磁共振、 红外光谱以及高分辨质谱等手段对产物结构进行了表征.     

双二苷酰胺从硝酸溶液中萃取Eu(Ⅲ)和Am(Ⅲ)

采用混合酸酐法合成了两种双二苷酰胺(bisdiglycolamide, BisDGA)萃取剂: N,N,N'',N''-四正辛基-N',N″-乙二基-双二苷酰胺(TOE-BisDGA)和N,N,N'',N''-四正辛基-N',N″-间苯二甲基-双二苷酰胺(TOX-BisDGA). 以磺化煤油和正辛醇混合溶液(体积比 90∶10)作稀释剂, 研究了它们在硝酸溶液中对Eu(Ⅲ)和Am(Ⅲ), 以及自身对HNO₃的萃取行为. 结果表明, 2种BisDGAs对HNO₃均有一定萃取, 当酸度不超过1.0 mol/L时, 二者形成1∶1型的萃合物. 随HNO₃浓度增加, Eu(Ⅲ)和Am(Ⅲ)的萃取分配比增加. 相同条件下, TOE-BisDGA对Eu(Ⅲ)和Am(Ⅲ)的萃取能力强于TOX-BisDGA. 斜率分析表明TOE-BisDGA和TOX-BisDGA与Eu(Ⅲ)和Am(Ⅲ)均形成2∶1型的萃合物. 温度升高, 萃取分配比下降, 萃取反应是放热反应. 2种BisDGAs对Eu(Ⅲ)的亲和力强于对Am(Ⅲ)的亲合力, 表明BisDGAs对Eu(Ⅲ)有一定的选择性. 同时, 研究了BisDGAs萃取Eu(Ⅲ)和Am(Ⅲ)的机理, 给出了表观萃取平衡常数和萃取反应热力学函数ΔH, ΔS和ΔG的值. 此外, 还对TOE-BisDGA和TOX-BisDGA与Eu(Ⅲ)形成的配合物进行了红外和紫外光谱分析.     

基于N,N'-双(3-吡啶基)-对苯二甲酰胺和1,3,5-苯三甲酸的二维Co(Ⅱ)金属有机骨架的合成、结构和磁性

在水热条件下,基于配体N,N'-双(3-吡啶基)-对苯二甲酰胺(3-bptpa)和1,3,5-苯三甲酸(1,3,5-H₃btc),合成了一例具有二维格子结构的钴(Ⅱ)MOF[Co(3-bptpa)(1,3,5-Hbtc)]·2H₂O(1),并进行了红外光谱(FT-IR)、元素分析(EDS)、差热-热重分析(DTA-TG)、X射线单晶衍射(XRD)和磁学表征。 结果表明,每个1,3,5-Hbtc^2-提供1个螯合配位羧基和1个桥连配位羧基与Co(Ⅱ)离子配位。 中心对称的二聚体[Co(3-bptpa)(1,3,5-Hbtc)]₂通过桥连配位的羧基连接成1D梯形链,相邻的梯形链通过3-bptpa与Co(Ⅱ)的配位作用连接为2D格子,从而形成CoN₂O₄变形八面体的配位构型。对配合物1在16~300 K的磁化率数据,使用八面体场下旋轨耦合的各向同性的单离子近似和分子场理论进行分析,Co(Ⅱ)离子表现强的旋轨耦合作用(λ=-100.4 cm^-1),相邻的Co(Ⅱ)离子之间通过桥连配位的羧基传递弱的反铁磁相互作用(zj'=-0.618 cm^-1)。     

异构多羧酸配体的两种Zn(Ⅱ)配位聚合物的水热合成和表征（英文）

利用异构的半刚性多羧酸配体3,5-二(3-羧基苯氧基)苯甲酸(3-H3BCP),3,5-二(4-羧基苯氧基)苯甲酸(4-H3BCP)和刚性双三唑配体4-(4-(4H-1,2,4-三唑-4-基)苯基)-4H-1,2,4-三唑(L)在相似的水热条件下与金属Zn(Ⅱ)离子反应,制得混合配体的配位聚合物{[Zn(3-HBCP)(L)]·0.5H2O}n(1)和[Zn(4-HBCP)(L)0.5]n(2)。配合物1为含有双核簇的(4,4)连接的二维网络结构,而配合物2为三重互穿的2D+2D→2D平行网络结构。通过X射线单晶衍射、元素分析、红外光谱、紫外光谱以及荧光光谱其进行了表征。     

新型含噻吩基8-羟基喹啉锌配合物的合成及光电性能

设计合成了含噻吩基的新型配体(E)-2-[2-(3-噻吩基)乙烯基]-8-羟基喹啉(4)及相应的锌配合物5, 产物结构经核磁共振、 红外光谱和元素分析进行表征. 利用X射线单晶衍射仪测定了中间体(E)-2-[2-(3-噻吩基)乙烯基]-8-乙酰氧基喹啉(3)和配体4的单晶结构, 结果表明中间体3晶体分子间并无明显的氢键作用, 分子间呈交错堆叠; 配体4分子之间由硫氢氧键弱作用相互排列形成网状结构. 通过核磁滴定及紫外和荧光滴定模拟了配体4在溶液中与金属锌的配位过程. 固体荧光寿命研究结果表明, 配合物5的荧光寿命为18.8 ms. 通过电致发光器件研究发现, 配合物5作为发光层具有良好的电致发光性能, 同时具有较好的电子传输能力.     

含氟8-羟基喹啉锌配合物的合成与发光性能

设计合成了2种含三氟甲基的8-羟基喹啉衍生物配体:(E)-2-[2-(3-三氟甲基苯基)乙烯基]-8-羟基喹啉(3a)、(E)-2-[2-(4-三氟甲基苯基)乙烯基]-8-羟基喹啉(3b)及其相应的锌配合物(4a)、(4b),并由1H NMR、IR、MS、元素分析确认了其结构。通过紫外滴定观察了金属锌与配体的配合过程,测定了它们在DMF溶液中的荧光性质;荧光光谱显示化合物3a、3b在DMF溶液中的λmax分别是491nm和513nm,4a、4b的λmax分别是585nm和599nm,而且改变三氟甲基的位置可以调节配合物的发光性能。     

三氮唑取代杯[4]芳烃配位聚合物的合成与荧光性能

利用四[1-(1, 2, 4-三氮唑基)甲基]间苯二酚杯[4]芳烃配体(TTR4A)在溶剂热的条件下合成了两个配位聚合物,[[Zn₂(TTR4A)(L)₂]·DMF·4H₂O]_n(化合物1) (DMF = N, N-二甲基甲酰胺)和[[Co(TTR4A)Cl₂]·DMA·H₂O]_n (化合物2) (H₂L = 4, 4’-联苯二甲酸) (DMA = N, N-二甲基乙酰胺)。通过单晶X射线衍射方法对这两个配位聚合物的结构进行了确定。利用红外、元素分析、粉末X射线衍射(PXRD)和热重表征手段对化合物1和2进行了表征。在化合物1中,四个L配体连接着四个Zn(Ⅱ)离子形成了环状的Zn₄L₄结构单元,该结构单元进一步地被TTR4A链接形成了一维链状结构。在化合物2中,TTR4A的四个三氮唑基团各连接一个Co(Ⅱ)离子形成二维层状结构。此外,我们对化合物1的荧光性能进行了研究,荧光测定表明固态条件下化合物1发出很强的荧光,并能够选择性地对Fe³⁺、Cr₂O₇²⁻和硝基苯分子产生响应。     

Crystal structure and luminescence property of ternary terbium p-aminobenzoic acid complexes with different second ligands

Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL₃(DMSO)(H₂O)]₂ (1), [TbL₃(DMF)(H₂O)]₂ (2) and [TbL₃(Bpy)(H₂O)]₂·2H₂O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L⁻ ligand and the characteristics of a second ligand, are discussed.     

两种具有螺旋结构的双核铜有机-无机配位聚合物的合成及表征

在水热和溶剂热条件下, 有机多齿羧酸4,4'-三苯胺二甲酸(H₂L)及含铜化合物分别与2,2'-联吡啶(bpy)和1,4-二(吡啶-4-甲氧基)苯(bpmb)反应, 合成了2种新型的含铜配位聚合物[Cu₂L(bpy)](1)和[CuL(bpmb)_0.5]·DMF(2). 通过X射线单晶衍射、 红外光谱、 元素分析、 热重和粉末X射线衍射分析等对其结构进行了表征. 结果表明, 化合物1属正交晶系, Pnma空间群, 其骨架为二维层状结构; 化合物2属单斜晶系, P2₁/c空间群, 具有{4⁴·6¹⁰·8}拓扑结构的三维网络.     

季铵盐型阳离子表面活性剂与牛血清白蛋白的相互作用

本文合成并表征了三种不同烷基链长度的季铵盐型阳离子表面活性剂：N-十二烷基-N-（2-羟乙基）-N,N-二甲基溴化铵（DHDAB）、N-十四烷基-N-（2-羟乙基）-N,N-二甲基溴化铵（THDAB）、N-十六烷基-N-（2-羟乙基）-N,N-二甲基溴化铵（CHDAB）。采用荧光光谱法、紫外-可见光谱法、动态光散射法和等温滴定量热法对三种表面活性剂与牛血清白蛋白（BSA）的相互作用进行研究。荧光光谱研究表明,三种表面活性剂主要与BSA分子内的色氨酸残基发生相互作用,导致蛋白质的构象发生变化,且表面活性剂烷基链越长,与BSA的相互作用就越强。BSA荧光猝灭的主要原因是静态猝灭,紫外光谱实验同样验证了静态猝灭的存在。等温滴定量热法结果表明低浓度的表面活性剂与BSA主要发生静电作用和疏水作用而放热。动态光散射结果表明高浓度的表面活性剂会使BSA结构被破坏。本文揭示了表面活性剂与BSA相互作用的机理,为表面活性剂的广泛应用提供了理论基础。     

Decorating poly(alkyl aryl-ether) dendrimers with metallacarboranes

A new family of polyanionic poly(alkyl aryl-ether) metallodendrimers decorated with four and eight cobaltabisdicarbollide units have been obtained in high yield by the ring-opening reaction of cyclic oxonium [3,3'-Co(8-(C(2)H(4)O)(2)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))] with alkoxides formed by deprotonation of terminal alcohols in the α,α'-bis[3,5-bis(hydroxymehyl)phenoxy]-p-xylene, α,α'-bis[3,5-bis(hydroxymehyl)phenoxy]-m-xylene, α,α'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-p-xylene, and α,α,'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-m-xylene dendrimers. The crystal structure of the precursor α,α'-bis[3,5-bis(chloromethyl)phenoxy]-p-xylene is also described. Final products are fully characterized by FTIR, NMR, UV-vis spectroscopies and elemental analysis. For metallodendrimers, the UV-vis absorptions have been a good tool for estimating the experimental number of cobaltabisdicarbollide units peripherally attached to the dendrimeric structure and consequently to corroborate the complete functionalization of the dendrimers.     

Spectral study of the structure of compartmental complexes of europium and copper

Compartmental complexes [EuH₂(fsa)₂en]Cl·3H₂O and [CuH₂(fsa)₂en]·0.5H₂O have been synthesized and characterized. The compartmental ligand (H₄(fsa)₂en) is N,N′-bis(3-carboxysalicy- lidene)ethylenediamine. Spectral study indicates that Eu(III) and Cu(II) are coordinated by the ---O₂O₂ coordinating atoms (outside) and the ---N₂O₂ coordinating atoms (inside), respectively. Since there is a considerable difference in the ligand field strength between the “outside” and “inside” coordination spheres, their different fluorescence properties have been investigated by photoacoustic spectroscopy and fluorescence spectroscopy.     

Synthesis and characterization of organo-soluble poly(amide-imide)s based on 1,2-bis[4-(trimellitimido)phenoxy]ethane and aromatic diamines

<正>New organo-soluble poly(amide-imide)s(PAIs) 8a-8f were prepared from newly synthesized 1,2-bis[4,4'-(trimellitimido) phenoxy]ethane 6 via direct polycondensation with various aromatic diamines.The diacid 6 was synthesized by the condensation reaction of 12-bis[4-atninophenoxy]ethane 4 with trimellitic anhydride 5 in acetic acid.All polymers were obtained in quantitative high yields with inherent viscosities of 0.48-0.61 dL/g.All of these polymers were highly soluble in organic solvents such as,N-methyl-2-pyrrolidone(NMP),dimethylformamide(DMF),N,N'-dimethylacetamide (DMAc) and dimethylsulfoxide(DMSO) at room temperature and were fully characterized by means of NMR spectroscopy, FTIR spectroscopy,elemental analyses,inherent viscosity,solubility test,specific rotation,differential scanning calorimetry (DSC) and thermogravimetric analysis(TGA).     

Lanthanide-based coordination polymers assembled from derivatives of 3,5-dihydroxy benzoates: syntheses, crystal structures, and photophysical properties

Two new aromatic carboxylic acids, namely, 3,5-bis(benzyloxy)benzoic acid (HL1) and 3,5-bis(pyridine-2-ylmethoxy)benzoic acid (HL2), have been prepared by replacing the hydroxyl hydrogens of 3,5-dihydroxy benzoic acid with benzyl and pyridyl moieties, respectively. The anions derived from HL1 and HL2 have been used for the support of a series of lanthanide coordination compounds [Eu(3+) = 1-2; Tb(3+) = 3-4; Gd(3+) = 5-6]. The new lanthanide complexes have been characterized on the basis of a variety of spectroscopic techniques in conjunction with an assessment of their photophysical properties. Lanthanide complexes 2, 4, and 6, which were synthesized from 3,5-bis(pyridine-2-ylmethoxy)benzoic acid, were structurally authenticated by single-crystal X-ray diffraction. All three complexes were found to exist as infinite one-dimensional (1-D) coordination polymers with the general formula {[Ln(L2)(3)(H(2)O)(2)]·xH(2)O}(n). Scrutiny of the packing diagrams for 2, 4, and 6 revealed the existence of interesting two-dimensional molecular arrays held together by intermolecular hydrogen-bonding interactions. Furthermore, the coordinated benzoate ligands serve as efficient light harvesting chromophores. In the cases of 1-4, the lowest energy maxima fall in the range 280-340 nm [molar absorption coefficient (ε) = (0.39-1.01) × 10(4) M(-1) cm(-1)]. Moreover, the Tb(3+) complexes 3 and 4 exhibit bright green luminescence efficiencies in the solid state (Φ(overall) = 60% for 3; 27% for 4) and possess longer excited state lifetimes than the other complexes (τ = 1.16 ms for 3; 1.38 ms for 4). In contrast to the foregoing, the Eu(3+) complexes 1 and 2 feature poor luminescence efficiencies.     

Synthesis and characterization of polyamides derived from (4-(4-(2, 6-diphenylpyridin-4yl)phenoxy)phenyl)-3, 5-diaminobezamide

New types of polyamides containing pendent triaryl pyridine groups were successfully synthesized by direct polycondensation of a symmetry diamine,（4-（4-（2,6-diphenylpyridin-4yl）phenoxy）phenyl）-3,5-diaminobezamide（DPDAB）, and various aromatic and aliphatic dicarboxylic diacids in NMP using triphenyl phosphate（TPP） and pyridine as catalyst. The diamine and all the prepared polyamides were fully characterized by using FT-IR,¹H-NMR,UV-Vis spectroscopy, fluorimetry and elemental analysis.The inherent viscosity of polyamides ranged from 0.45 dL/g to 0.68 dL/g.All the polymers exhibited solubility in common polar aprotic solvents such as NMP,DMAc,DMF,DMSO,pyridine,HMPA,and even in less polar solvents such as THF and m-cresol at room temperature.Thermal properties of polyamides were evaluated by means of DSC,DMTA and TGA.These polymers showed glass transition temperatures（T_g） in the range of 138-210℃. Their initial decomposition temperature（T_i） varied from 265℃to 310℃under N₂.The dilute solution（0.2 g/dL） of polyamides in DMF exhibited fluorescence emission withλ_max in the range of 470-550 nm.     

系列Ln(Ⅲ)配聚物的合成、结构及近红外发光性能

通过水热反应合成5种结构新颖的配聚物:{[Ln_2(1,3-bdc)_3(H_2O)_4](DMF(H_2O}_n[Ln=Pr(1),Nd(2),Gd(3)]和{[Ln_4(1,3-bdc)_6(H_2O)_4(DMF)](DMF(2H_2O}_n[Ln=Er(4),Ho(5)](1,3-bdc:间苯二甲酸,DMF:N,N-二甲基酰胺)。通过单晶X射线衍射、红外光谱、紫外-可见-近红外(UV-Vis-NIR)光谱、荧光光谱等技术手段对产物的结构和性能进行了表征。结果表明,配聚物1~3是同构的,属单斜晶系,P2(1)/n空间群;配聚物4、5是同构的,属三斜晶系,P-1空间群。在晶体中,间苯二甲酸根采用多样的配位模式,使配聚物呈现多维的结构。除配聚物4,其余均呈现Ln(Ⅲ)的特征NIR发光,并与其UV-Vis-NIR吸收光谱相关联。