四(4-氨基苯基)卟啉及其金属配合物的表面光电压性能的研究

以对硝基苯甲醛和吡咯为原料,硝基苯为溶剂,反应合成了四(4-硝基苯基)卟啉(TNPP),将TNPP用二氯化锡还原后得到了四(4-氨基苯基)卟啉(TAPP),并进一步用TAPP与金属盐反应合成了其金属配合物。利用紫外可见光谱、红外光谱、核磁共振氢谱对合成产物进行了结构表征。并研究了这些卟啉化合物在不同外加电场条件下的表面光电压谱(SPS),结果表明,TAPP及其金属配合物都具有良好的光电性能,且其Soret带与Q带的光伏响应强度随外加正电场光伏响应强度的增加而增强,随外加负电场光伏响应强度的增加而减弱,具有P-型半导体的特征。     

偶氮卟啉的合成、表征与光电导性能

以对硝基苯甲醛和吡咯为原料合成了对硝基苯基卟啉,再经硝基还原、重氮化和偶合反应合成了两种多偶氮连接的卟啉化合物,并用核磁、质谱、红外光谱及紫外-可见光谱对化合物进行了结构表征.分别以这些卟啉化合物为电荷产生材料制备了功能分离型双层光电导体,并对其光电导性能进行了研究.结果表明,偶氮卟啉的光敏性明显优于四苯基卟啉,其光敏性分别为1.8和28.8 lx•s.     

壳聚糖固载的锌卟啉的合成及表征

以苯甲醛、丙酸和吡咯为原料合成四苯摹卟啉(TPP),以TPP为原料,合成四苯基锌卟啉,利用紫外-可见光谱、红外光谱和核磁共振波谱3种表征手段,证实了TPP和四苯基锌卟啉的合成.用天然含氮高分子壳聚糖同载锌卟啉,以期提高锌卟啉的稳定性及催化能力,利用红外光谱技术,证实了壳聚糖固载的锌卟啉的合成.其合成为进一步探讨金属卟啉及壳聚精固载的会属卟啉的仿生催化能力奠定了基础.     

四苯基卟啉及其衍生物的合成

以吡咯为起始原料,在丙酸的催化下,与苯甲醛缩合成四苯基卟啉;用质量分数为65%的浓硝酸选择性单硝化TPP,并用氯化亚锡还原得氨基化TPP。结果表明:采用丙酸催化,反应2.0h,四苯基卟啉产率为24.6%,单硝化TPP产率为54.1%,还原TPP产率为46.1%。该反应合成路线和具体实验条件对相关化合物的合成具有较好的借鉴意义。     

四羟基苯基锰卟啉的制备及其电化学性质研究

本文采用了优化路径分别合成出了四羟基苯基卟啉(THPP)和及其衍生物四羟基苯基锰卟啉(THPP-Mn)两种化合物,并对它们的结构与性能进行了表征。THPP和THPP-Mn在丙酮溶剂中的紫外可见光谱表明,相对于THPP,THPP-Mn的紫外可见光谱中的Soret带发生红移,吸收峰从419 nm移到476 nm,THPP-Mn的Q带吸收峰的个数减小,这是因为卟啉生成配合物后对称性增强而使吸收峰数目减少的缘故。电化学测试结果表明,四羟基苯基锰卟啉有一对明显的氧化还原峰,具有较好的氧化还原可逆性,并且随着扫描速率从10 mV/s增加到200 mV/s,其氧化峰从1.32 V逐渐增加到1.53 V,还原峰从0.94 V减少到0.74 V。因此,四羟基苯基锰卟啉具有较好的电化学性能,在储能材料领域具有很好的应用前景。     

胡椒醛缩合卟啉化合物的合成及其光谱性能

以胡椒醛及羟基芳香醛为原料与吡咯在丙酸中回流,合成了6种卟啉化合物,其结构用1HNMR,IR,UV-V is和ESI-MS确定。与四苯基卟啉(TPP)相比,胡椒醛的引入增大了卟啉环的共轭性,使几种化合物的光学吸收波长均发生不同程度的红移,其中,Soret带最大红移11 nm;同时,胡椒醛的引入缩小了基态与激发态之间的能极差,化合物荧光发射波长发生1~5 nm的红移。     

6种取代四苯基卟啉化合物的合成

以二甲苯为溶剂,氯乙酸为催化剂,硝基苯为氧化剂,由取代苯甲醛与吡咯发生缩合反应合成了6种取代四苯基卟啉化合物,并用紫外-可见光谱(UV-Vis)和红外光谱(IR)对所合成的产物进行了结构表征.考察了酸性催化剂和氧化剂对卟啉合成收率的影响,使卟啉收率得到了大幅提高,其中对位取代四苯基卟啉的合成收率＞45%,邻位取代四苯基...     

β-硝基和β-氨基取代卟啉及其金属配合物的合成和光谱分析

本文以5, 10, 15, 20-四苯基卟啉(TPP)为原料,采用金属盐硝化法区域选择性合成了β-硝基-5, 10, 15, 20-四苯基卟啉(β-NO2-TPP)及其铜配合物。以β-硝基-5, 10, 15, 20-四苯基卟啉为原料,二氯化锡作为还原剂,氮气保护下在冰醋酸-氯仿混合溶剂中,较温和条件下制备了β-氨基-5, 10, 15, 20-四苯基卟啉(β-NH2-TPP)及铜配合物。利用MS、1H NMR、UV-Vis和IR对所合成的化合物结构进行了表征,研究了紫外和荧光光谱性质及产生单线态氧的能力。     

金属卟啉配合物光解水制氢的性能研究

金属卟啉配合物是一类广泛应用于光催化的材料。文章以对羟基苯甲醛、苯甲醛与吡咯为原料,合成了单羟基苯基卟啉化合物,并且与镍、铜、钴进行配位,得到3种金属配合物。在光照条件下,研究这些化合物分解水产氢的性能。     

β-4，4′-二羟基联苯卟啉的合成及其生物活性研究

以伊硝基四苯基金属卟啉为原料,将4,4′-二羟基联苯引入四苯基卟啉的卢位得到一系列4,4′-二羟基联苯卟啉,通过紫外光谱、红外光谱、质谱及核磁共振氢谱等对该卟啉化合物进行了结构表征,并考察了其生物活性。结果表明,4,4′-二羟基联苯引入到四苯基卟啉的β位,使其Soret带一定程度上红移;β-4,4′-二羟基联苯卟啉具有明显的产生单线态氧的能力;光照条件下。β-4,4′-二羟基联苯卟啉对pBR322质粒DNA有明显的切割作用;β-4,4′-二羟基联苯卟啉可能是以外部自堆积的方式与CT—DNA发生作用的。     

Metal-Ion Type Effect on the Crystal Structure and Optical Properties of 2,2′-bipyridine Complexes of Pb(II) and Cd(II)

To investigate the effect of metal ion type on the crystal structure and optical and thermal behaviors of coordination compounds, two homometal and one heterometal 2,2′-bipyridine complexes of Pb(II) and Cd(II) have been synthesized and characterized by elemental analysis, PXRD, FT-IR and single crystal X-ray diffraction. Crystal structure analysis of heterometal coordination polymer, [Pb₂Cd(2,2′-bipy)₄(NO₃)₆]_n, displays the attendance of a centrosymmetric 1D coordination polymer that crystallizes in the triclinic system with the space group of \({\text{p}}_{1}^{ - }\). Thermal behavior of prepared coordination compounds was examined under air atmosphere by thermogravimetric analysis. The study of optical properties of compounds showed that metal ion type of coordination compounds is influential on their photophysical properties. Moreover, heterometal coordination polymer was doped into a PVK:PBD blend in two different concentrations as a light emitting material in the fabrication of two organic light-emitting diodes.     

偶氮化合物的光电导性能的研究

本文合成了五种双偶氮颜料 ,它们是以芴酮为桥基 ,以含有五种不同取代基的色酚为偶合剂的化合物 .测定了这些化合物的吸收光谱和X射线衍射光谱 ;分别以这五种偶氮颜料为电荷产生材料制备了功能分离型双层光电导体 ,并对它们的光电导性能进行了研究 .     

基于巯基三氮唑及其衍生物构筑配合物的研究进展

巯基三氮唑是一种含硫氮杂环有机化合物,由于具有多个配位点和较强的配位能力以及衍生物的多样性, 近些年在配位化合物、医药等方面受到广泛研究。本文按照取代基数目的不同将巯基三氮唑衍生物分为疏基三 氮唑、单取代巯基三氮唑、多取代巯基三氮唑、多臂巯基三氮唑衍生物,并按照分类系统地总结了近些年来这 类配体及其金属配合物的合成方法和结构特征方面的研究成果,同时介绍了其金属配合物在药物、功能材料方 面的应用。最后依据巯基三氮唑及其衍生物构筑配合物的研究现状,从配体、金属离子两方面对巯基三氮唑未 来的研究方向进行了展望。     

Studies on the thermal stabilization enhancement of ABS; synergistic effect by triphenyl phosphate and epoxy resin mixtures

Triphenyl phosphate (TPP) and its analogs are known to be the most effective flame retardant for acrylonitrile-butadiene-styrene copolymer (ABS) among various phosphorus-based compounds. But, its evaporation temperature is quite lower than the processing temperature of ABS. Therefore, it is inevitable to avoid a considerable amount of TPP to evaporate during processing. In order to overcome this undesirable phenomena, we incorporated various epoxy resins to TPP as coflame retardants and a series of ABS/TPP/epoxy compounds were made from them and their flame retardancy were evaluated by measuring the limiting oxygen index (LOI) values. Our results showed that the incorporated epoxy is very effective in suppressing the evaporation of TPP from the compounds and the LOI value as high as 38 is obtained. It is also found that more the epoxide ring contents in epoxy resins, the higher the LOI value of the compounds. The reason for this finding was postulated to come from the interaction between phosphoric acid and carboxylic acid generated from epoxy during thermal degradation. And some direct evidences from FTIR experiments were presented even though they were not conclusive. Moreover, the LOI values of quaternary mixtures of ABS, tetra-2,6-dimethyl phenyl resorcinol diphosphate, TPP, and epoxy resins were evaluated and that the same synergism of epoxy incorporation on flame retardancy was also found for them.     

Synthesis,characterization and spectroscopic studies of two new schiff-base bithienyl pendant-armed 15-crown-5 molecular probes

Two new ligands provided with a 15-crown-5 as a receptor unit and bithiophen unit as an emissive probe have been synthesized and characterized in order to evaluate the coordination capabilities and their sensor effect. Ligand L1 presents an aromatic crown ether moiety that is directly linked to the imine-2,2′-bithiophene π–conjugated system, and ligand L2 is constituted by an aliphatic crown ether moiety that is linked to the same imine-2,2′-bithiophene system through a methylene unit. Solid metal complexes of Ni(II), Pd(II), Hg(II) and Na(I) have been synthesized using both macrocyclic compounds, and have been studied in solution in the presence of the same metal ions. All solid compounds have been characterized by common analytical and spectroscopic techniques. The sensorial effect has been studied using absorption, emission and MALDI-TOF-MS spectroscopies.     

The Role of Weak Intermolecular Interactions in the Assembly of a Series of d<Superscript>10</Superscript> Metal Coordination Polymers Based on <Emphasis Type="Italic">N,Nʹ</Emphasis>-Bis-Pyridin-3-Ylmethylene-Naphtalene-1,5-Diamine Ligand; Ultrasonic Synthesis,Spectroscopic and Structural Characterization

The motivation of this work is to highlight factors that influence the supramolecular structures of d¹⁰ metal coordination polymers. Two novel Hg(II) and Cd(II) 1D coordination polymers (CPs) have been constructed from metal iodide and a N,N′-bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand using conventional methods. Our analyses reveal the substantial role of weak hydrogen bonds and π–π stacking interactions in the assembly of these series of compounds. These compounds were studied using X-ray crystallography, infrared spectroscopy and X-ray powder diffraction. The supramolecular structures of these two compounds were compared with two structures that have been published recently. These coordination polymers in nano-size were synthesized under ultrasonication and their morphology were characterized using scanning electron microscopy (SEM).     

苯乙烯基三苯胺化合物的高收率合成与光导性能

以亚磷酸三乙酯与氯化苄或对甲基氯化苄反应制备W ittig试剂,再与N,N-二(甲)苯基氨基苯甲醛反应,高收率制备了N,N-二(4-甲基苯基)-4-〔2-(4-甲基苯基)乙烯基〕苯胺(Ⅱa)、N,N-二(4-甲基苯基)-4-(2-苯基乙烯基)苯胺(Ⅱb)、N,N-二苯基-4-〔2-(4-甲基苯基)乙烯基〕苯胺(Ⅱc)、N,N-二苯基-4-(2-苯基乙烯基)苯胺(Ⅱd)4种空穴传输材料,收率分别达96.4%、92.1%、89.4%、92.6%。产物通过元素分析、红外光谱和质谱等进行了表征。以Y-TiOPc为电荷产生材料,合成化合物为空穴传输材料,制备了有机光导体,并进行了光电性能测试,化合物Ⅱa、Ⅱb和Ⅱc光敏性均在0.04~0.05 lx.s,是性能优异的电荷传输材料。