以氢键组装的铜(Ⅱ)、锌(Ⅱ)卟啉超分子构象

考察了 5 -对 - (间羰基苯甲酸 ) -氨基苯基 - 1 0 ,1 5 ,2 0 -三苯基卟啉锌 ( )配合物 ( Zn( m-CPTPP) )、铜 ( )配合物 ( Cu( m- CPTPP) )及 ( Zn( m- CPTPP) )与 5 -对 - (对羰基苯甲酸 ) -氨基苯基 -1 0 ,1 5 ,2 0 -三苯基卟啉铜 ( ) ( Cu( p- CPTPP) )通过氢键的超分子自组装行为。上述两体系都通过氢键自组装成超分子。 Zn( m- CPTPP) - Cu( m- CPTPP)体系存在卟啉环间的π-π堆积作用     

对氯苯基卟啉-氨基酸及其锌配合物的合成和表征

为了探索氯的空间位置及不同的氨基酸对卟啉 -氨基酸化合物性能的影响 ,合成了 5 - [4-(3 -酪氨酸丙氧基 )苯基 ]- 1 0 ,1 5 ,2 0 -三 (4-氯苯基 )卟啉 ,5 - [4- (3 -组氨酸丙氧基 )苯基 ]- 1 0 ,1 5 ,2 0 -三(4-氯苯基 )卟啉 ,两种新型的尾式卟啉 -氨基酸化合物及其锌配合物 ,用元素分析 ,紫外 -可见光谱 ,红外光谱 ,核磁共振氢谱 ,质谱确证了其结构 ,并测试了其荧光光谱     

卟啉锌/锰配合物的合成与表征

用5,10,15,20-四(4氯苯基)卟啉或5-(4-羟基苯基)-10,15,20三(4-氯苯基)卟啉与四水氯化锰、醋酸锌反应,合成了5,10,15,20-四(4-氯苯基)卟啉锌、5,10,15,20-四(4-氯苯基)卟啉锰、5-(4-羟基苯基)-10,15,20-三(4-氯苯基)卟啉锌、5(4-羟基苯基)-10,15,20-三(4-氯苯基)卟啉锰四种金属卟啉,并用UV-Vis、IR对其结构进行了表征。     

Model systems for fluorescence and singlet oxygen quenching by metalloporphyrins

Next-generation photodynamic therapy agents will minimize extraneous phototoxicity by being active only at the target site. To this end, we have developed a model system to systematically investigate the excited-state quenching ability of a number of metalloporphyrins. Central metal ions that prefer four-coordinate, square planar orientations (Ag(II), Cu(II), Ni(II), Pd(II), and Zn(II)) were used. Porphyrin dimers based on 5-(4-aminophenyl)-10,15,20-triphenylporphyrin and comprising both a free base porphyrin and a metalloporphyrin covalently linked through a five-carbon alkyl chain were synthesized. The fluorescence and singlet oxygen quantum yields for the dimers were probed at 630 and 650 nm, respectively, resulting in the excitation of only the free base porphyrin and allowing a comparison of the quenching efficacy of each central metal ion. These results demonstrate that metalloporphyrins can serve as efficient quenchers, and may be useful in the design of novel light-activated therapeutic agents.     

水体系中含卟啉基团的两亲高分子的自组装行为和性质的研究

在文中合成了两种不同的卟啉单体5-(4-acryloyloxyphenyl)-10,15,20-tris(4-carboxylphenyl)porphyrinate zinc(II)(ZnAOTCPP)和5-(4-acrylo-yloxyphenyl)-10,15,20-tris(4-methoxycarboxylphenyl)porphyrinate zinc(II)(ZnMeAOTCPP),它们分别与丙烯酰胺(Acrylamide,AM)聚合得到含有卟啉基团的两亲高分子.与对应的单体相比,含有三羧酸卟啉基团的高分子在水中形成了一个新的紫外吸收峰和一个新的荧光发射峰,而含有三羧酸甲酯卟啉基团的高分子除此之外在更长波的方向上还另外出现了一个新的紫外吸收峰和一个新的荧光发射峰.随着高分子水溶液浓度的提高,高分子中卟啉基团的光谱性质的变化趋势显示高分子在水中的自组装行为可以分为分子间缔合和分子内缔合的两种情况.此外,实验结果显示含有三羧酸甲酯卟啉基团的高分子相对于含有三羧酸卟啉基团的高分子更加有利于卟啉缔合物的形成.     

新型L-苏氨酸尾式卟啉及其锌(II)配合物合成与表征

为了探索手性金属卟啉配合物的结构与功能 ,用 L-苏氨酸和 5 -[邻 -(2 -溴乙氧基 )苯基 ]-1 0 ,1 5 ,2 0 -三苯基卟啉为原料合成了一种新型 L-苏氨酸尾式卟啉及其锌 (II)配合物 ,通过元素分析、红外光谱、化学分析和质谱等对其进行了结构表征。测试并研究了它们在 40 0 0～ 40 0 cm- 1 范围内的傅里叶变换红外光谱 ,对主要谱带进行了经验归属     

Novel meso-substituted porphyrins: Synthesis, characterization and photocatalytic activity of their TiO2-based composites

Two series of novel meso-substituted porphyrins, namely 5,10,15,20-tetra[4-(3-phenoxy)-propoxy]phenyl porphyrin, the structural analogue 5,10,15,20-tetra[2-(3-phenoxy)-propoxy]phenyl porphyrin and their Co(II) Cu(II) and Zn(II) complexes were synthesized. The compounds were characterized using various spectroscopic techniques and their molecular structure was proposed based on density functional theory calculations. The diverse properties of the porphyrin derivatives result from the different stereochemistry of the particular substituents at the meso site on the macrocycle and are controlled also by the coordinated metal. The ¹H NMR spectrum of the free-base porphyrin showed a complicated spin-splitting. The photocatalytic activities in degradation of 4-nitrophenol were investigated using polycrystalline TiO₂ impregnated with the porphyrins and metalloporphyrins. The Cu(II) porphyrin was a more effective sensitizer than other metal containing compounds (M = Co, Zn) as well as the free-base. Photocatalytic activity was also influenced by spatial positions of the substitutions on the porphyrin molecules.     

Novel 5-benzazolyl-10,15,20-triphenylporphyrins and β,meso-benzoxazolyl-bridged porphyrin dyads: Synthesis, characterization and photophysical properties

Novel 5-benzazolyl-10,15,20-triphenylporphyrins and β,meso-benzoxazole-linked diporphyrins were synthesized through La(OTf)₃ catalyzed reaction of newly prepared 5-(3,4-diaminophenyl)-10,15,20-triphenylporphyrin or 5-(3-amino-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with aromatic aldehydes in 1,2-dichlorobenzene. On metalation with zinc acetate, freebase β,meso-benzoxazole-linked diporphyrin was successfully converted to the Zn-Zn diporphyrin complex in good yield. The synthesized porphyrin analogues were characterized using electronic absorption, IR and ¹H NMR spectroscopy in addition to mass and elemental analyses. The fluorescence studies of 5-benzazolyl-10,15,20-triphenylporphyrins showed efficient intramolecular energy transfer from the pyrene and fluorene subunits to the porphyrin core. In addition, the fluorescence quenching observed in β,meso-benzoxazolyl-bridged porphyrin dyads was attributed to the possible nonplanarity of a component of the diporphyrins. The freebase-Ni diporphyrin complex underwent strong emission quenching in comparison to that of freebase diporphyrin and dizinc diporphyrin analogues.     

Self-assembly of novel tris(p-carboxyphenyl) porphyrin monomer and its copolymers with acrylamide in aqueous media

The novel porphyrin monomer 5-(4-acryloyloxylphenyl)-10,15,20-tris(4-carboxyphenyl)porphyrinate zinc(II) (ZnAOTCPP) and its corresponding sodium salt (ZnAOTCPP-Na) were synthesized. The latter compound exhibited a new band in excitation spectra due to formation of porphyrin aggregates in water, which were derived from its surface-activity when the concentration was higher than its critical association concentration (CAC). The porphyrins were copolymerized with acrylamide (AM) to prepare water-soluble copolymers with random and micro-blocky structures, which all displayed very new absorption and fluorescence emission bands in the long wavelength region compared with the porphyrin monomer. Furthermore, the micro-blocky copolymer exhibited an additional new absorption band at even longer wavelength region compared with the random copolymer. The experimental results and analysis showed that the porphyrin units in the random copolymer chains self-assembled to form porphyrin association complexes by hydrophobic association and π-π stacking interactions, and covalent restrictions of polymer chains in the micro-blocky copolymer.     

尾式亮氨酸卟啉锌配合物的合成和光谱性质研究

合成了尾式亮氨酸卟啉—— [5- (对亮氨酸丁氧苯基 ) - 1 0 ,1 5,2 0 -三苯基卟啉及其锌 ( )的配合物 ( Zn[Leu- TPP]) ,用元素分析、红外光谱、电子吸收光谱和激光拉曼光谱等手段对其结构进行了表征。研究了吡啶 ( Py)、4-甲基吡啶 ( 4 - Me Py)、4-醛基吡啶 ( 4 - CHOPy)、4-氨基吡啶 ( 4 - Am Py)等化合物对 Zn[Leu- TPP]电子光谱的影响     

新型Salen-卟啉金属配合物催化剂的研究

以5-对氨基苯基-10,15,20-三苯基卟啉和水杨醛为原料,合成水杨醛缩氨基四苯基卟啉,分别加入Ni(NO3).26H2O和Mn(OAc)2.4H2O,经络合反应,合成了两个同时具有卟啉结构和Salen结构的配合物3a和3b,产率分别为75%和80%,各化合物均通过UV-Vis,IR,1HNMR,元素分析进行表征。将配合物3a和3b应用于环己烷的催化氧化,环己烷的转化率分别达到了8.25%和12.45%。     

Metal complexes as potential ligands: The deprotonation of aminephenolate metal complexes

The cationic nickel, copper and zinc complexes of tris-(2-hydroxybenzyl)-aminoethylamine (H6TrenSal) have been deprotonated using potassium hydroxide. The nickel complex can be sequentially deprotonated to form a series of compounds namely, [(H6TrenSal)Ni]⁺, [(H6TrenSal)Ni] and “[(H6TrenSal)Ni]K”. The latter is isolated as a mixture of species namely [{(H6TrenSal)Ni}K(EtOH)]₂, [{(H6TrenSal)Ni}K(EtOH)₂-μ-OH₂]₂ and [{(H6TrenSal)Ni}K(EtOH)₂-μ-EtOH]₂, which co-crystallise in a roughly 50:27.5:22.5 ratio. In contrast the deprotonation of [(H6TrenSal)M]⁺ (M = Cu, Zn) results in the formation of tetrameric complexes [({(H6TrenSal)Ni}K(OH₂)₂)₄(μ₄-OH₂)].     

尾式苏氨酸卟啉及其锌配合物的合成和光谱性质

合成了尾式苏氨酸卟啉——[5-(对苏氨酸丁氧苯基)-10，15，20-三苯基卟啉及其锌(Ⅱ)的配合物(Zn[Thr-TPP])，用元素分析、红外光谱、电子吸收光谱和激光拉曼光谱等手段对其结构进行了表征，研究了咪唑(Im)对Zn[Thr TPP]电子吸收光谱的影响。     

芳基取代丙烯腈为骨架的芪类化合物的合成

对合成结构较简单的4种以芳基取代丙烯腈为骨架的芪类化合物的常用合成方法进行了研究。以取代苯甲醛和取代苯乙腈为原料,在氮气保护、甲醇钠作催化剂等条件下,通过一步缩合反应,高收率得到(Z)-2-(3,4-二甲氧苯基)-3-(4-甲氧苯基)丙烯腈(Ⅰ)、(Z)-2-(3,4-二甲氧苯基)-3-(3,4-二甲氧苯基)丙烯腈(Ⅱ)、(Z)-2-(3,4-二甲氧苯基)-3-(4-二甲氨基苯基)丙烯腈(Ⅲ)、(Z)-3-(3,5-二甲氧苯基)-2-(4-甲氧苯基)丙烯腈(Ⅳ),实测收率分别为98.3%、96.0%、83.4%及88.8%。     

5-(2-羟基-1-萘醛4-萘基亚胺)-10,15,20-三萘基卟啉及其金属配合物的合成与表征

合成了标题化合物,并与醋酸盐反应,得到了它的锌、铜、钴3种金属配合物.采用元素分析、紫外.可见光谱、红外光谱、核磁、质谱等手段对该配体和配合物进行了表征.     

尾式1,3-二噁烷基卟啉及其金属配合物的合成与表征

在特定的条件下以桂皮醛、二苯基壬四烯酮和氢溴酸为原料合成出了一种环状β-卤代缩醛类化合物—— 2 -( 2 -溴 -2 -苯乙基 ) -1 ,3-二烷 ,在无水碳酸钾的存在下与 5 -对羟基苯基 -1 0 ,1 5 ,2 0 -三苯基卟啉反应合成出了一种新型尾式卟啉—— 5 -{对 -[2 -( 2 -苯乙基 ) -1 ,3-二烷 ]氧基苯基 } -1 0 ,1 5 ,2 0 -三苯基卟啉 ,同时合成了其锌、钌、钯金属配合物 ,并通过电子光谱、元素分析、1 HNMR、IR等光谱手段进行了表征     

Syntheses and investigation of thermal properties of copper complexes with azo-containing Schiff-base dyes

In the present study a series of azo dyes: 5-((4-pentyloxyphenyl)azo)-salicylaldimine-N-R (R = phenyl, 4-methoxyphenyl, cyclohexyl) and related copper(II) bis chelates have been synthesized and characterized by IR, NMR, mass spectroscopies and elemental analyses. The thermal stability of free ligands and related copper(II) bis(chelate) was studied by using differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA). The differences in the thermal stability were related to the structure of free ligands and copper complexes and decomposition products were characterized according to their X-ray diffraction pattern.     

Synthesis of a porphyrin–C60 dyad for potential use in solar energy conversion

A convenient procedure for the synthesis of a new porphyrin–C₆₀ dyad via the reaction between 5-(4-aminophenyl)-10,15,20-tris(4-methoxyphenyl) porphyrin and a C₆₀ carboxylic acid is described. The results of preliminary photoelectrochemical studies on nanostructured SnO₂ electrodes coated with the new dyad suggest that the resultant substrate is suitable for solar energy conversion devices.     

镍卟啉配合物[Ni(bpy)(t-BuOPTPP)]的合成与表征

报道了一种新型尾式卟啉化合物5-(4-叔丁氧基苯基)-10、15、20-三苯基卟啉[H2(t-BuPTPP)]及其Ni(bpy)^2 配合物的合成,并通过元素分析、红外光谱、核磁共振氢谱及紫外可见光谱等对其结构进行了表征。     

尾式谷氨酸卟啉及其金属配合物的合成

合成了5－[对－N－谷氨酸丁氧基）苯基]－10，15，20－三（对氯苯基）卟啉（H2L）及其配合物MLCl(M=Co，Fe,Mn)，并对它们进行了元素分析，UV－cis，荧光光谱，IR和^1H NMR等结构表征。催化实验发现，除配体外，3种配合物在分子氧氧化苯甲醛的反应中具有催化作用。