几种卟啉及其配合物合成方法的改进

本文首先改进了meso位有强推电子基团的四-[4-(N,N-二甲基)苯胺基]卟啉(TDMAPPH~2)的合成方法.在此基础上, 改进了最近报道的一种新型水溶性卟啉四-[4-(N,N,N-二甲基, 丙磺酸基)苯胺基]卟啉(TDMAPPTPSH~2)的合成, 进而合成了系列水溶性金属卟啉(M'TDMAPPTPS, M'=Co,Cu,Zn,Mg,Mn,Ni).并由IR,UV-vis光谱法和元素分析得到确证.     

1,1′-二(N-水杨酰腙乙基)二茂铁及其过渡金属(Ⅱ)的配合物

本文合成了1,1'-二(N-水杨酰腙乙基)二茂铁及其过渡金属配合物,ML·nH_2O[M=Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)和Cd(Ⅱ)],并用元素分析、UV、IR、~1H NMR、TG-DTA和摩尔电导进行了表征.配体以烯醇式通过亚胺基氮原子和酰胺基氧负离子与金属离子配位,按摩尔比1:1结合.Ni(Ⅱ)配合物有一分子DMF配位.大部分配合物都比配体热稳定性高.     

一系列新的双光子聚合引发剂:合成与非线性光学性质

通过无溶剂反应,合成了四种具有D-π-D(D-供体,π-共轭体系)结构的光聚合引发剂,即4,4′-双[2-(4-N,N-二乙胺基)-苯乙烯基]联苯(BDEVB)、4,4′-双[2-(4-N,N-二丙胺基)-苯乙烯基]联苯(BDPVB)、4,4′-双[2-(4-N,N-二丁胺基)-苯乙烯基]联苯(BDBVB)和4,4′-双[2-(4-N-甲基-N-羟乙基胺基)-苯乙烯基]联苯(BMHVB),并利用1HNMR,IR和元素分析进行了表征,同时研究了它们在不同溶剂中的单光子和双光子荧光.实验结果表明:不同的电子供体使其单光子荧光和双光子吸收截面具有不同的变化趋势.     

四-(对甘-缬二肽苯基)卟啉及其过渡金属配合物的研究

本文以四-(对氨基苯基)卟啉和N-氯乙酰缬氨酸为原料，在DMF中首次合成了一种新型的含二肽基团的四苯基卟啉，四-(对甘-缬二肽苯基)卟啉(H₂L)，及其Mn(Ⅲ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)配合物MnLCl, FeLCl, CoL, NiL, CuL, ZnL，用元素分析、红外光谱、电子光谱、荧光光谱、氢核磁共振谱和激光拉曼光谱进行了表征，研究了这些新型配合物与含N、S碱的轴向加合性质。     

新型β,β-桥连双卟啉的合成及其光敏活性研究

以1,6-二溴己烷为桥连试剂, 2-(1-羟基萘基)-5,10,15,20-四苯基卟啉及其Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)配合物为原料, 合成了4个新型β,β-桥连双卟啉. 以1,3-二苯基异苯并呋喃(DPBF)为猝灭剂, 测试了双卟啉及其Ni(Ⅱ), Zn(Ⅱ)配合物在光照条件下产生单线态氧的能力, 并研究了4个双卟啉化合物在光照和无光照条件下对pBR322质粒DNA的切割能力(用凝胶电泳)和对金黄色葡萄球菌(ATCC 25923)的光敏抑菌活性. 结果表明, 新型双卟啉光敏剂具有较好光敏活性, 产生的活性氧能有效杀灭金黄色葡萄球菌.     

一种1,8-萘酰亚胺Cr~(3+)离子荧光探针的研究

以4-硝基-1,8-萘酐、N,N-二甲基乙二胺为主要原料合成了一种荧光探针:4-(2′-N,N-二甲基氨基乙基)氨基-N-(2-N,N-二甲基氨基)乙基-1,8-萘酰亚胺(DDN)。研究了其紫外可见吸收和荧光发射光谱。考察了Fe3+,Cr3+,Mn2+,Ni2+,Zn2+,Cu2+和Co2+离子对该化合物荧光发射光谱的影响,结果表明Cr3+离子能使DDN荧光显著增强。滴定实验结果推测DDN与Cr3+的结合比为1∶2。在DDN浓度为1.0×10-5mol/L时,Cr3+浓度在5.0×10-7~2.0×10-5mol/L范围内,DDN荧光强度(F)与Cr3+离子浓度[Cr3+]呈良好的线性关系,线性方程为F=9430.3527+14600.2973[Cr3+],相关系数r=0.9976。检测限为4.3×10-7mol/L。     

纳米晶TiO2电极上半菁衍生物光敏染料

合成了具有不同共轭链长度的吡啶盐类及喹啉盐类半菁染料(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]吡啶鎓盐(P1)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]吡啶鎓盐(P2)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]喹啉鎓盐(Q1)以及(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]喹啉鎓盐(Q2).研究了它们的光物理性质，并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池.与含有乙烯基共轭桥的染料P1和Q1相比，含有丁二烯基共轭桥的染料P2和Q2在甲醇和氯仿中的最大吸收均发生一定程度的红移，而且吸收光谱变宽.这两类染料都能很好地吸附于TiO2电极上.在比较了四个染料的吸收光谱、摩尔消光系数以及在TiO2电极表面的吸附量后，发现Q1具有最好的光电转化性质.     

仲胺配合物的合成、晶体结构及与DNA作用的研究

合成了一种新颖三齿配体(L),N-(4-甲基苯)-N’-(2-(4-甲基苯氨基)乙基)乙烷-1,2-二胺,并制备了它的四种过渡金属配合物,结合元素分析、红外、1 HNMR和摩尔电导,确定配合物的组成为[ML(NO3)2](M=CuⅡ,CoⅡ,NiⅡ,ZnⅡ).用X-ray单晶衍射解析了Zn-L和Ni-L的单晶结构.通过紫外、荧光光谱研究了这四种金属配合物与小牛胸腺DNA的相互作用,根据结果推断出配合物与DNA的作用方式可能均为静电结合.Cu-L,Co-L,Ni-L,Zn-L与DNA的结合常数分别为:3.34×104,7.65×103,2.15×104,2.40× 104.     

金属卟啉化合物光催化反应研究 Ⅱ.周边取代与轴向配位对金属卟啉光敏化反应的影响

本文研究了中-四(对三甲胺基苯基)金属卟啉(MeTPI,Me=H_2,Zn(Ⅱ),Cu(Ⅱ),Ni(Ⅱ),Mn(Ⅲ),Co(Ⅲ))光敏化还原甲基紫精(MVI_2)反应,用动力学方程参数a,诱导时间t_i和初始反应速率V_0来衡量光敏剂的优劣.同时讨论了不同的取代基以及不同的轴向配体对光敏剂光敏性的影响.结果表明:Zn(Ⅱ)TPI的光敏性较好;含氮芳香有机碱对光敏剂起“增敏”作用,并且通过引入带有正电荷的轴向配体,使“增敏”效果更加显著,同时发现,脂肪胺起“降敏”作用.     

水溶性卟啉配合物的合成及光敏化行为

在低沸点的氯仿溶剂中合成了中-四(对二甲基丙磺酸基氨基)苯基卟啉(简记为H₂TPS),在乙酸溶剂中合成了相应的金属卟啉[简记为MeTPS,Me=Zn(Ⅱ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅲ),Mn(Ⅱ)],并进行了表征。TEOA-MeTPS-MV²⁺-DMSO(H₂O)(75:25,V/V)体系的光敏化还原MV²⁺反应的研究结果表明,Zn(Ⅱ)TPS、Mn(Ⅱ)TPS及H₂TPS是较好的光敏剂,且以Zn(Ⅱ)TPS为最好。     

2,2''''—双〔2—(邻甲酰肟苯氧基)乙基〕醚与过渡金属配合物的合成及性质研究

含氮配位原子的希夫碱型化合物在分析化学、合成化学、药学等方面有广泛的应用。近十多年来,随着新药物的研制和生物无机化学的发展,其研究正在不断深入。肟类化合物在结构上与希夫碱型化合物主要不同之处是在于它与氮原子相连的基团是羟基,它在适当的条件下可参与金属配位或形成氢键,研究其配位模式有较重要的理论意义。我们合成了一个新的含醚氧链的双肟化合物,2,2＇—双[2—(邻甲酰肟苯氧基)乙基]醚(H_2BFO)。本     

Synthesis and Spectral and Coordination Properties of meso-Tetraarylporphyrins

Russian Journal of Organic Chemistry - 5,10,15,20-Tetrakis(3,5-dibromophenyl)porphyrin and 5,10,15,20-tetrakis(3-bromo-4-methoxy-phenyl)porphyrin have been synthesized, and their complexing...     

Solubility of Tetra(pyrid-3- and 4-yl)porphines and Their Complexes with <Emphasis Type="Italic">d</Emphasis>-Metals in Chloroform and Ethanol

The solubility of 5,10,15,20-tetra(pyrid-3- and 4-yl)porphine isomers and their coordination compounds with d-metals in the temperature range of 298–318 K is studied. Patterns of the dissolving of porphyrin ligands and the metal complexes they form with Co(II), Cu(II), and Zn(II) in chloroform and ethanol depending on the nature of the metal and the position of the nitrogen atom in the pyridyl substituent of the porphyrin molecule are discussed. The thermodynamic parameters of dissolution are calculated for the investigated compounds.     

Synthesis of Vinylene-Co,N-Linked Multi(porphyrin)s by the Addition of Free-Base Porphyrins to a C(2)H(2) Complex of Cobalt(III) Porphyrin and Their Oxidative Rearrangement to Vinylene-N,N'-Linked Multi(porphyrin)s

The nucleophilic addition reaction of a pyrrole nitrogen of free-base porphyrins to a pi-complexed acetylene ligand in a cationic Co(III) porphyrin intermediate afforded good yields of vinylene-Co,N'-linked bis(porphyrin)s, (Por)Co(III)-CH=CH-(N-Por)H(2). N-substituted porphyrin free bases are N-vinylated regioselectively at the pyrrole adjacent to the original N-substituted pyrrole in this reaction. Tris- and tetrakis(porphyrin)s have been prepared by reacting a vinylene-N,N'-linked bis(meso-tetraarylporphyrin) with (OEP)Co(III)(H(2)O)(2)ClO(4) (OEP: octaethylporphyrin dianion) and acetylene. The tetrakis(porphyrin) proved to be a 1:1 mixture of C(i)()- and C(2)-symmetric regioisomers. These organometallic Co(III) complexes underwent facile oxidative migration of the Co-bound vinyl group to a porphyrin pyrrole nitrogen when treated with Fe(III) salts or HClO(4) to provide moderate to good yields of Co(II) vinylene-N,N'-linked multi(porphyrin) complexes. (Vinylene-N,N')bis(porphyrin) free bases with combinations of different porphyrins have been obtained by this procedure. The homobinuclear (2Co(II), 2Cu(II), and 2Zn(II)) and heterobinuclear (Co(II)Cu(II) and Co(II)Zn(II)) complexes have been prepared and characterized spectroscopically. The single-crystal X-ray analysis of (CH=CH-N,N')[(OEP)Co(II)Cl][(TPP)Zn(II)Cl] (TPP: meso-tetraphenylporphyrin dianion) showed a face-to-face structure with an average inter-ring separation of 4.39 ? (triclinic P&onemacr;; Z = 2; a = 14.806(4), b = 18.703(10), c = 13.796(3) ?, alpha = 97.69(3), beta = 99.57(2), gamma = 96.74(3) degrees ).     

Asymmetrical porphyrins. I. Synthesis,characterization and physicochemical properties of phenyl/4-benzyloxyphenyl 5,10,15,20-substituted porphyrins

A complete series of five phenyl/4-benzyloxyphenyl 5,10,15,20-substituted porphyrin has been synthesized, characterized by analysis, R_f values, and proton-nmr spectroscopy (pmr). Their physicochemical properties, namely ir spectra, absorption spectra, emission spectra, excited state life-times, pK₃ values, reduction potentials, and kinetics of Cu(+2) insertion, have been determined. Attempts have been made to correlate these physicochemical properties with the structures of the porphyrins.     

Synthesis of Glucoside Bonded Metal Porphyrins

Enzyme catalyzed reaction often has high selectivity and efficiency under mild conditions. However, disadvantage of enzyme catalysts is the difficulty of recovery. Metalloporphyrin plays an important role in biological system such as redox reaction, electron transfer,oxygen transportation and charge separation etc.1,2 Metalloporphyrins as superoxide dismutase (SOD) mimics have showed the ability of catalyzing the redox reaction of some harmful radicals , such as O2·―, ·OH. Grove and co-…     

Supramolecular self-assembly of a fluorinated Zn porphyrin. Molecular structure of a two-dimensional network of amine-functionalized,hexacoordinated Zn porphyrins

[5,10,15,20-Tetrakis(4-n-propylamino-2,3,5,6- tetrafluorophenyl)porphyrinato]zinc(II) self-assembles into a two-dimensional supramolecular array in which each porphyrin is linked to four orthogonally-oriented chromophores.     

Preparation, characterization and thermal studies of some transition metal ternary complexes

Ternary complexes of Co(II), Ni(II), Cu(II) and Zn(II) with nitrilotriacetic acid as a primary ligand and glycine as secondary ligand were prepared in slightly acid medium. Their molecular masses were determined by acid-base titration against standard potassium hydroxide solution. Their molecular structures were found to be [M (HNTA)(glyH)(2H₂O)]. Thermogravimetric analysis confirmed this structure and that the water present is coordinated to the central metal atom. UV-Vis spectra showed that the complexes have octahedral symmetry. IR spectra suggested the presence of intermolecular hydrogen bonding. This phenomenon was supported by mass spectra. The ionization constants of these complexes, as diprotic acids, were determined.     

两亲性卟啉的合成及其L—B膜

早期L-B膜的研制主要着眼于长碳链脂肪酸及其衍生物。近来,由于对膜性能的特殊要求,人们把注意力转向丁二炔、酞菁和卟啉衍生物。本文用四一(N,N-二甲基氨基苯基)卟啉(TDMAPP)与溴代十六烷反应得到两亲性的含有4个长碳链的澳化四-(4-