新型偶氮苯金属配合物的合成与性能

合成了新型偶氮苯金属配合物。分别采用光谱分析、热分析及X射线衍射测试技术对产物进行了表征和测试。结果表明,连接偶氮苯和金属配合物之间碳链的长度对该化合物的相转变和荧光特性具有特殊的影响。该系列化合物在紫外光和热作用下具有99%以上的偶氮苯顺-反异构化反应效率;具有290和560 nm这2个波段的荧光发射光谱。由其中1个金属配合物分散在聚甲基丙烯酸甲酯网络而形成的介质可作为全息信息存储材料而实现全息图像的写入和读出。     

生色冠醚研究

用４－甲基－７－羟基－８－甲酰基香豆素与三种４′－氨基苯并冠醚和４′，４″－二氨基二苯并－１８－冠－６反应，合成了四个新的Ｓｃｈｉｆ碱型苯并冠醚。它们都是有色化合物，具有强荧光性质。在这些Ｓｃｈｉｆ碱型苯并冠醚溶液中加入过渡金属盐时，不同程度地发生荧光猝灭现象，生成的配合物也是荧光化合物；而加入碱金属和碱土金属盐时，则荧光性质几乎不受影响     

对硝基苯甲酰芳肼的合成及氧化脱氢研究

取代酰肼化合物是制备偶氮化合物的原料,是一类非常重要的有机化合物,具有广泛的应用价值。它可以和金属形成稳定配合物,对聚烯烃等高分子材料的“铜害”有良好的防护作用,被称为金属减活剂[1];在照相技术方面,苯酰肼类化合物加入氯化银乳胶层中,可提高其光敏感性,使对比度增大     

基于四元羧酸钙配位聚合物的合成、结构及其荧光性能（英文）

通过水热法合成了一种结构稳定的金属有机框架化合物{[Ca(atba)_4·2H_2O]·H_2O}_n(H_4atba=偶氮苯-3,3',5,5'-四羧酸).运用X射线单晶衍射、红外谱图及X射线粉末衍射对其进行了结构表征.晶体结构测试表明该配合物通过{Ca_2(CO_2)_2}结构单元形成了一维链状结构,继而通过配体之间的连接形成二维层状结构,进一步通过共价键构筑成三维结构.荧光光谱分析表明,标题化合物对L-组氨酸具有选择性识别作用.     

壳聚糖固定化亚铁Schiff碱配合物的研究

利用具有多种生物医用活性的高分子壳聚糖的轴向配位作用合成了壳聚糖-N-亚水杨基氨基酸Schiff碱亚铁配合物,采用IR光谱、元素分析、荧光光谱、紫外-可见吸收光谱和热分析等分析手段对配体及高分子配合物进行了表征,推测了其结构.以核黄素光化学氧化-羟胺-偶氮比色法研究了该化合物对超氧离子自由基的清除能力.结果表明,壳聚糖固定化的N-亚水杨基氨基酸Schiff碱亚铁配合物对超氧离子自由基的清除能力有所降低,但仍具有较强的抑制作用.     

具有亲油性及近红外光吸收特性的金属细菌卟吩的合成与表征

在四氢呋喃中加入金属卟吩、 强碱(无水氢化钠)和金属盐MX_n(M=Cu, Ni, Pd), 合成了细菌卟吩的5种过渡金属配合物, 该方法减少了反应时间, 提高了反应产率. 通过紫外-可见光谱、 核磁共振氢谱、 质谱等方法对所合成的化合物进行了表征, 并研究了其光学性质. 结果表明, 细菌卟吩在近红外区有明显的吸收峰, 且具有较高的强度, 相比于细菌卟吩配体, 金属配合物吸收光谱中的Q_x和Q_y带均发生了明显的红移. 细菌卟吩配体与锌配合物具有发光性质, 为Q_y(0,0)荧光, 而铜、 镍等金属配合物并没有检测到荧光峰.     

几个8-氨基喹啉新衍生物与钴(Ⅱ)的显色和荧光反应的比较研究

系统研究了所合成的七个8-氨基喹琳-5-偶氮苯类和三个8-(对甲苯磺酸氨基)喹啉-5-偶氮苯类新衍生物与Co(Ⅱ)的显色和荧光反应。发现了试剂取代基对配合物显色增敏和荧光增感的规律,探讨了H_2O_2对荧光增感的机理。     

新型Cd(Ⅱ)-MOF的合成及对4-硝基苯胺的高效识别

采用新型1,3,5-三(1H-苯并[d]咪唑-2-基)苯(TBB)配体及2,5-二羟基对苯二甲酸(H₂dhtp)线性配体, 以Cd(Ⅱ)离子为中心节点, 构筑了具有新型拓扑结构(unj)的手性金属-有机框架材料[Cd(TBB)(dhtp) ](配合物1). 该配合物具有较强的光致发光性能, 可分散在溶液中荧光检测硝基配合物等污染物. 其中, 4-硝基苯胺对配合物1具有高效的荧光猝灭能力, 检测限可低至0.145 mg/L, 并具有较好的选择性.     

非对称双极性(D-π-A)吡啶Salophen席夫碱锌/镍配合物的合成、表征、线性及非线性光学性质研究

通过Still偶联反应合成了吡啶取代的香草醛(1a和1b)。以过渡金属离子(Zn2+和Ni2+)作为模板,以单亚胺席夫碱2和吡啶基香草醛为原料合成和表征了新的非对称双极性(D-π-A)Salophen金属配合物(3a、3b和3c)。测定了这些金属配合物的线性和三阶非线性光学(双光子吸收,TPA)性质。双极性的Salophen金属配合物的发射光谱在可见光范围内(486~516 nm),荧光寿命4.51 ns~5.18 ns,荧光量子产率在4.3%~5.3%之间。衰减时间测试表明,荧光寿命是在纳秒级范围,这表明该发射来自单线态。对这些化合物进行了热重分析,结果表明3a、3b和3c都是热稳定的,起始分解温度(Td)为333~374℃。使用开孔Z-扫描方法在800 nm处用100 fs脉冲的激光对这些双极性的Salophen金属配合物的TPA截面σ(2)进行了测试,最高可达1 403 GM,其值为目前已知席夫碱金属配合物较高值之一。测试表明,锌的Salophen金属配合物具有良好的荧光量子产率、巨大的TPA截面σ(2)、很高的热稳定性以及锌配合物公认的低毒性。因这些配合物可以被近红外或红外波长的光激发,这种光可以有效地穿透生物组织同时减轻细胞损伤,所以Salophen锌配合物作为双光子荧光发色团在生物体成像中有潜在的应用。     

新型配合物[Zn(dib)(H2O)3]SO4·2H2O的水热合成、晶体结构和荧光性质

由水热法合成了锌化合物[Zn(dib)(H2O)3]SO4.2H2O(1)(dib=1,4-二咪唑基苯),并对其进行了元素分析、IR及X-射线衍射法表征。晶体结构表明:配合物1属于正交晶系,Fddd空间群。配合物1是由桥联配体1,4-二咪唑基苯连接成一维链状结构,该一维链被氢键拓展成三维超分子结构。配合物1的荧光测试研究表明它具有蓝色荧光。     

Studies on thermal behavior of some antibacterial copper (II) complex compounds with a dibiguanide derivative ligand

The thermal behavior of six complex compounds of Cu(II) with chlorhexidine as ligand was investigated. The complexes are obtained from chlorhexidine diacetate and copper (II) chloride, bromide and acetate, respectively, in metal:ligand molar ratio 1:1 and 2:1. Thermal decomposition evidenced several well-defined steps as desolvation, anionic moieties release and the ligand cleavage for all complexes. The final residue is in all cases copper (II) oxide.     

Photoresponsive Carbon-Azobenzene Hybrids: A Promising Material for Energy Devices

Advancements in renewable energy technology have been a hot topic in the field of photoresponsive materials for a sustainable community. Organic compounds that function as photoswitches is being researched and developed for use in a variety of energy storage systems. Azobenzene photoswitches can be used to store and release solar energy in solar thermal fuels. This review draws out the significance of azobenzene as photoswitches and its recent advances in solar thermal fuels. The recent developments of nano carbon templated azobenzene, their interactions and the effect of substituents are highlighted. The review also introduces their applications in solar thermal fuels and concludes with the challenges and future scope of the material. The advancements of solar thermal fuels with cost effective and desired optimal properties can be explored by scientists and engineers from different technological backgrounds.     

Kinetic Studies of Solvent and Pressure Effects on the Thermal Isomerization of Palladium Dithizonate

IntroductionThe photo-and thermo-chromisms of organometallic compounds have been intensivelystudied during thelast1 0 years.Meriwetheretal.[1 ,2 ] examined the chromic behaviorofmet-al-dithizone(phenyldiazenecarbothionic acid2 -phenylhydrazide) complexesin detail.From thekinetic and infrared studies,they showed thatthe central metal of a dithizonate complex de-termined the photochemical stability,the rate of the thermal return reaction,and the colorofthe dithizonate complex.As reported by Mer…     

Influence of helical twisting power on the photoswitching behavior of chiral azobenzene compounds: applications to high-performance switching devices

Five photochromic chiral azobenzene compounds and one nonphotochromic chiral compound were synthesized and characterized by IR, 1H NMR spectroscopy, and elemental analysis. Cholesteric liquid crystalline phases were induced by mixing of the nonphotochromic chiral compound and one of the photochromic chiral azobenzene compounds in a host nematic liquid crystal (E44). The helical pitch of the induced cholesteric phase was determined by Cano's wedge method and the helical twisting power (HTP) of each sample was thus determined. The helical twisting powers of azobenzene compounds were decreased upon UV irradiation, due to trans-->cis photoisomerization of azobenzene molecules. Among the azobenzene compounds synthesized in our study, Azo-5, with isomannide (radical) as chiral photochromic dopant, showed the highest HTP and contrast ratio (Tmax/Tmin). Photoswitching between compensated nematic phase and cholesteric phase was achieved through reversible trans<-->cis photoisomerization of the chiral azobenzene molecules through irradiation with UV and visible light, respectively. Transmission rates (contrast ratios) increased with decreasing helical pitch length in the induced cholesteric phase. The influence of helical twisting power on the photoswitching behavior of chiral azobenzene compounds is discussed in detail.     

Thermal properties of mercury(II) and palladium(II) purine and pyrimidine complexes

Six solid Pd(II) and Hg(II) complexes of some purines and pyrimidines have been prepared and characterized by elemental analyses, IR, UV–Vis spectra, magnetic measurements, and thermal analyses. The data suggest tetrahedral and square planar geometries for mercury and palladium complexes, respectively. The thermal behavior of the complexes has been studied applying TG, DTA, and DSC techniques, and the thermodynamic parameters and mechanisms of the decompositions were evaluated. The ?S* values of the decomposition steps of the metal complexes indicated that the activated fragments have more ordered structure than the undecomposed complexes, and/or the decomposition reactions are slow. The thermal processes proceeded in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing small molecules such as H₂O, HCl or C=O. The palladium adenine complex is ended with the metal as a final product. However, the thermal reactions of the other five palladium and mercury pyrimidines complexes are ended with metal bonded to O, N, or S of the pyrimidine ring.     

Synthesis of azoxybenzene-SbCl5 complexes and their selective ortho-wallach rearrangement

When an equimolar solution of various azoxybenzenes and SbCl₅ in carbon tetrachloride were mixed, a 1:1 complex immediately deposited as orange crystals in high yield. The thermal reaction of these complexes in inert solvents gives o-hydroxy-azobenzene selectively. On the contrary, other Lewis acids such as TiCl₄, AlCl₃, FeCl₃ and ZnBr₂ failed to give an isolatable complex with azoxybenzene, and their direct thermal reaction with azoxybenzene resulted in deoxygenation to yield azobenzene as a main product.     

Stereochemistry of new nitrogen containing heterocyclic compounds.; X. Supramolecular structures and stereochemical versatility of polymeric complexes

New polymeric complexes of Cu(II), Co(II), Ni(II) and UO2(II) with 5-(2(1)-carboxyphenylazo)-8-hydroxyquinoline (LH2) have been prepared and characterized on the basis of analytical, magnetic, 1H NMR, EPR and electronic spectral studies. Tentative structures for the polymeric complexes are proposed. The important infrared (IR) bands and the main 1H NMR signals are assigned and discussed relative to the molecular structure. EPR spectrum of copper(II) complex has been studied with a view to assigning their stereochemistries. Various EPR parameters have been calculated. Each metal has six-coordinates in an octahedral environment. The ligand acts as a dibasic (bis-bidentate chelating agent coordinating through CN, N=N, COOH and OH groups by replacement of a proton from the two latter groups. Considerable interest has also been focused on the synthesis of the azo compounds and its polymeric metal complex due to its wide potential applications. The thermal decomposition behavior of the complexes is also discussed.     

Synthesis and characterization of dicyclopalladated complexes of azobenzene derivatives by experimental and computational methods

A series of doubly cyclopalladated complexes of azobenzene and its unsymmetrical substituted derivatives, namely, {LPdCl(mu-AZB)LPdCl}, where AZB is azobenzene, 4-methylazobenzene, 4-aminoazobenzene, or 4-(dimethylamino)-4'-nitroazobenzene, while L is N,N-dimethylformamide, dimethylsulfoxide, or pyridine, have been prepared. Their structural and spectroscopic properties were determined by X-ray diffraction analysis as well as by (1)H NMR, IR, UV-vis, and fluorimetric studies. Experimental results were rationalized by quantum chemical calculations. Crystal structures of several complexes have been resolved, and for the first time, it was demonstrated that the cyclopalladation may take place at the azobenzene aromatic ring having the strong electron-withdrawing substituent at the para position. In all cases, the metalated carbon and N,N-dimethylformamide or dimethylsulfoxide ligands are mutually trans, whereas the pyridine ligands are in the cis arrangement. cis/trans isomerism in the isolated compounds is explained by comparing the calculated energies of isomeric structures. All of the complexes absorb strongly in the visible region, and according to time-dependent density functional theory calculations, most of the absorptions can be attributed to intraligand pi --> pi* or metal-to-ligand charge-transfer transitions. The fluorescence emission was observed for the complexes with 4-aminoazobenzene or 4-(dimethylamino)-4'-nitroazobenzene. The aromaticity of palladacycles is evaluated by several aromaticity indices and related to relevant experimental findings.     

冠醚配合物的研究XV.若干席夫碱及仲胺型双冠醚和碱金属离子的配位反应

本文运用微量电导滴定及计算机拟合技术，研究了若干席夫碱及仲胺型双冠醚和碱金属离子的配位反应，测定了配合物的组成及稳定常数，并对实验结果进行了讨论。