Meso-四(对甲基-苯基)卟啉锌的合成及其光电性能

采用改进“Alder法”制得meso-四(对甲基 苯基)卟啉（TMPP）; TMPP络合锌离子合成了meso-四(对甲基-苯基)卟啉锌（TMPP-Zn）,收率21.22%,其结构和性能经FL, UV-Vis, ¹H NMR, IR和HR-MS(ESI)表征。溶剂化效应研究结果表明：TMPP-Zn在非质子非极性溶剂甲苯中有较强的发光性,强度为186.5561,在极性溶剂乙腈中发光性较弱,强度仅136.9312。聚集发光性能测试结果表明：水含量增加,发光性先增强后减弱,水含量90% 时发光性最好。循环伏安测试及单线态氧测试结果表明：TMPP-Zn能级差为1.98,能隙较高,10 min发光强度达2.8×10⁶。     

新型-meso-四(4-十四氨基甲酰苯基)卟啉及其-金属（Co）配合物的合成与液晶性能

对羧基苯甲醛和吡咯经缩合反应制得meso-四(4-羧基苯基)卟啉(1); 1与氯化亚砜反应得meso-四(4-氯甲酰基苯基)卟啉(2); 2与n-十四胺反应制得meso-四(4-十四氨基甲酰苯基)卟啉(3); 3与CoC_l2经配位反应合成了meso-四(4-十四氨基甲酰苯基)卟啉钴(4)。 3和4为新化合物,其结构经U-Vis, ¹H NMR和IR表征。偏光显微镜和DSC检测结果表明： 3和4具有液晶性能。     

新型meso-四(4-十四氨基磺酰苯基)卟啉及其配合物的合成与液晶性能

以吡咯和苯甲醛为原料制得meso-四苯基卟啉(1);1经氯磺化得meso-四(4-氯磺苯基)卟啉(2);2与十四胺反应制得meso-四(4-十四氨基磺酰苯基)卟啉(3);3与醋酸镉经配位反应合成了meso-四(4-十四氨基磺酰苯基)镉卟啉(4)。3和4为新化合物,其结构经UV-Vis,1H NMR和IR表征。偏光显微镜和DSC检测结果表明:3和4均具有液晶性能。     

强磁场对四苯基卟啉及其Co(Ⅱ)/Zn(Ⅱ)配合物的影响

为研究强磁场对卟啉类化合物的影响,以四苯基卟啉(TPP)为研究对象,比较分析了无外加磁场和强磁场条件下TPP的结晶,及Co~(2+)、Zn~(2+)与TPP的配位反应。采用X射线粉末衍射测试不同磁场强度下获得的TPP晶体,紫外分光光度计快速测定了不同磁场强度下配合物产率,并分析了配位反应的动力学。TPP的结晶度随磁场强度的增强而提高,晶体尺寸随磁场强度的增加而增大;随磁场的增强,四苯基钴卟啉(CoTPP)和四苯基锌卟啉(ZnTPP)的产率下降,但两者的反应动力学不受磁场影响,其反应速率随磁场强度提高而下降。由研究结果可知,强磁场有利于四苯基卟啉的结晶取向,四苯基卟啉在溶液中垂直于磁场取向是配位反应速率降低的主要原因,随磁场强度的增加,四苯基卟啉的取向程度提高。     

meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质

锌卟啉配合物;合成;meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质     

阴、阳离子型水溶性卟啉的有效合成

以meso-四(4-吡啶基)卟啉和meso-四(4-羟基苯基)卟啉为原料,三乙二醇单甲醚单元取代和锰离子配位作为功能性修饰手段,按照优化的反应条件,高效合成了吡啶基阳离子型和磺酸基阴离子型水溶性卟啉化合物.该类方法操作简单、收率高、反应条件温和,为同类型水溶性卟啉的合成提供了很好的合成方法.     

新型meso-四(4-N-n-十二胺基磺酰苯基)四苯并卟啉的合成及其液晶性能

苯乙酸锌和邻苯二甲酰亚胺反应制得meso-四苯基四苯并卟啉锌(1);1酸化得meso-四苯基四苯并卟啉(2);2经氯磺化生成meso-四(4-氯磺基苯基)四苯并卟啉(3);3与n-十二胺反应合成了一种新型的苯并卟啉类化合物--meso-四(4-N-n-十二胺基磺酰苯基)四苯并卟啉(4),其结构经UV-Vis,<'1>H...     

金属卟啉化合物光催化反应研究(Ⅳ)─四苯基钴卟啉光助还原O2反应

研究了不同的有机溶剂中四苯基钴卟啉(Co(Ⅱ)TPP)的光助还原O₂反应,详细讨论了溶剂效应和有机碱的轴向配位效应对光还原反应的影响,同时对反应机理进行了探讨。结果表明,溶剂的极性越大或有机碱的轴向配位能力越强时,光还原O₂反应的速率越大。     

meso-四(间烷氧基苯基)卟啉及其金属配合物的合成、表征和液晶性能研究

1987年Gregg等[1]合成了八酯取代卟啉及其Zn配合物并研究了其液晶性,1990年Shimichi等[2]报道了对-烷氧取代型四苯基卟啉(n=10,12)及其Co,Zn配合物(n=10)的液晶性,这些现象引起了人们对卟啉类化合物液晶性能研究的极大兴趣[3],我们在前文[4～6]报道了meso-四(对烷氧苯基)卟啉及其金属配合物的合成、表征和液晶性研究,但目前仍无meso-四(间烷氧基苯基)卟啉及其金属配合物的液晶性能的报道.本文合成了meso-四(间烷氧基苯基)卟啉及其铜、钴、锌配合物四个系列40个化合物,其中未见文献报道的新化合物35个;研究了其合成、分离、纯化方法;对于长链烷氧基取代的间位卟啉配体及其金属配合物,我们采用石油醚-无水甲醇混合溶剂重结晶和冰盐浴长时间冷冻的方法,首次得到这四个系列化合物的晶体或固体,在偏光显微镜下有明显的双折射现象.我们采用1HNMR,MS,IR,UV,元素分析等分析测试表征手段确证了这些化合物的结构,研究了这四个系列化合物的结构与1HNMR,IR,UV,MS的波谱关系及判据,报道和解析了间位长链烷氧基取代的四苯基卟啉铜配合物的1H NMR研究结果.     

TTP-钴构型的测定和meso-四(3,4-次甲二氧基苯基)卟啉的合成及其与镉的显色反应

本文对TTP-钴的构型进行了测定,证明其中位的4个苯环与卟啉环不在同一平面上,二者已不能发生共轭效应,所以取代基对卟啉环的影响较小,用改变取代基来提高试剂的灵敏度效果必然不大,本文合成了新型卟啉——meso-四(3,4-次甲二氧基苯基)卟啉(简称TMDOPP),并对其与镉显色反应分光光度法进行了研究,结果表明,此法灵敏度高(ε=4.9×     

Spectral and photochemical properties of tetraphenylporphyrin tetrasulfonate supported on modified montmorillonite nanoparticles

A photocatalyst that effectively sensitizes the oxidation of 9,10-diphenylanthracene in toluene under irradiation with visible light has been prepared by the treatment of cationic surfactant-modified montmorillonite nanoparticles with a solution of meso-tetrakis(4-sulfonatophenyl)porphyrin. Reaction quantum yields and singlet oxygen generation probability have been determined. The shifts and intensity changes observed for the absorption bands of meso-tetrakis(4-sulfonatophenyl)porphyrin in the catalyst as compared with aqueous solutions are associated with solvation effects. The meso-tetrakis(4-sulfonatophenyl)porphyrin triplet state has been detected using the laser photolysis technique, and the rate constant of its quenching by oxygen on the surface of nanoparticles has been measured.     

Studies of porphyrin zinc compounds intercalated into V<Subscript>2</Subscript>O<Subscript>5</Subscript> xerogel

The intercalation of meso-tetrakis(4-pyridyl)porphyrin zinc, the cationic salts of meso-tetrakis(N-methylpyridinium-4-yl)porphyrin zinc, and zwitterionic meso-tetrakis-[N-(3-sulfonatopropyl)pyridinium-4-yl]porphyrin zinc from aqueous solutions as well as of meso-tetrakis(N-methylpyriclinium-4-yl)porphyrin zinc from pyridine solutions into V₂O₅ xerogel was studied. The intercalation complexes obtained were characterized by X-ray diffraction analysis, TG analysis, IR, and UV reflectance spectroscopy.     

Electrocatalytic Hydrogen Evolution by Water-Soluble Cobalt (II), Copper (II) and Iron (III) meso-Tetrakis(carboxyl)porphyrin

Three water-soluble carboxyl metalloporphyrins, cobalt (II), copper (II) and iron (III) meso-tetrakis (carboxyl) porphyrin were prepared and applied as homogeneous electrocatalysts for hydrogen evolution reaction (HER) with acetic acid, trifluoroacetic acid, p-toluene sulfonic acid and water as proton sources. Cyclic voltammetry (CV) results revealed the HER underwent different routes for these metalloporphyrins. Electrocatalysis tests in buffer solution of pH=7.0 showed the TOFs of cobalt (II), copper (II) and iron (III) meso-tetrakis (carboxyl) porphyrin were 184.78, 160.28 and 184.87 mol⁻¹ ⋅ h⁻¹ and the faradaic efficiency were 94.37 %, 93.01 % and 96.98 % at an overpotential of 788 mV, respectively. These results indicate the synthesized metal carboxyl porphyrins have good electrocatalytic activity for HER.     

Porphyrin system containing [2.2]paracyclophane units

Meso-tetrakis([2.2]paracyclophanyl)porphyrin was obtained from [2.2]paracyclophanecarbaldehyde and pyrrole. Replacement of phenyl groups in meso-tetraphenylporphyrin by paracyclophanyl substituents remarkably influences the electronic structure of the molecule, causing bathochromic shifts of all uv-vis absorption bands, and changing the ring current of the porphyrin core. The shifts in the electron spectrum are substantially greater than those observed for other porphyrin derivatives characterized by their extended π-electron systems, such as meso-tetrakis(2-phenylethenyl)porphyrin and meso-tetrakisbiphenylporphyrin.     

Iron porphyrins-catalysed oxidation of α-alkyl substituted mono and dimethoxylated benzyl alcohols

The mechanisms of oxidation of a series of a-alkyl substituted mono and dimethoxylated benzyl alcohols catalysed by mesotetrakis(4-N-methylpyridynium)porphyrin iron (III) chloride (FeTMPyPCl) and meso-tetrakis(4-sulfonatophenyl)porphyrin iron (III) chloride (FeTSPPCl) in aqueous solution with KHSO₅ as oxygen atom donor and by meso-tetrakis(pentafluorophenyl)-porphyrin iron (III) chloride (FeTPFPPCl) in dichloromethane employing iodosylbenzene as oxidant have been investigated. In the highly polar aqueous medium an electron transfer mechanism is operating. With FeTMPyPCl, which is a much more efficient catalyst than FeTSPPCl due to the presence of stronger electron withdrawing substituents, formation of side-chain oxidation products accompanies generation of nuclear oxidation products. In the low polar solvent dichloromethane, two competing mechanism have been suggested: hydrogen atom transfer and formation of a complex between the active species iron-oxo porphyrin radical cation and the substrate.      

MS/MS Fragmentation Behavior Study of meso-Phenylporphyrinoids Containing Nonpyrrolic Heterocycles and meso-Thienyl-Substituted Porphyrins

Free base and cobalt(II) complexes of six meso-tetraphenylporphyrinoids containing nonpyrrolic heterocycles and of three meso-thienylporphyrins were investigated using electrospray ionization tandem mass spectrometry (ESI-MS/MS). Their fragmentation was studied in a quadrupole ion trap as a function of the porphyrinoid macrocycle structure and compared with the fragmentation behavior of the benchmark compound meso-tetraphenylporphyrin. In situ oxidation of the neutral cobalt(II) complexes under ESI conditions produced singly charged cobalt(III) porphyrinoid ions; the free bases were ionized by protonation. For the porphyrinoids with an intact porphyrin core, the major fragmentation pathways observed were the losses of the meso-substituent (for meso-phenyl groups) and characteristic fragmentations of one or more meso-substituents (for the meso-thienyl group). Complex fragmentation pathways were observed for porphyrinoids with modifications to the porphyrin core but chemically reasonable structures could be assigned to most fragments, thus delineating general patterns for the behavior of pyrrole-modified porphyrins under CID conditions.

Electrocatalytic Reactions by an Iron Porphyrin/Polypyrrole Modified Electrode Monitored by Electrochemical Quartz Crystal Microbalance

Electropolymerization of pyrrole in aqueous solution is monitored by electrochemical quartz crystal microbalance (EQCM) during potential scan. The film formation process on the electrode is reflected by the frequency decrease for the quartz oscillator as a function of time. The film growth rate is greatly enhanced in the presence of iron(III) meso-tetrakis(3-sulfonatomesityl)porphyrin, which carries 3- of charge. The metalloporphyrin is trapped and remains intact in the polypyrrole films. The ion transport property through the iron porphyrin/polypyrrole film is the reverse of that for pure polypyrrole. Electroreduction of dioxygen and electrooxidation of alkenes are parallel to those in the solution state.     

Chiral memory and self-replication study of porphyrin and bilirubin aggregates formed on polypeptide matrices

Porphyrin heteroaggregates composed of meso-tetrakis(N-methylpyridinium-4-yl)porphinatocopper(II) and meso-tetrakis(4-sulfonatophenyl)porphyrin formed in the presence of a polyglutamic matrix possess chiral memory and an ability to self-replicate their supramolecular structures. By means of electronic circular dichroism spectroscopy, it has been shown that the self-replication process is not influenced by changes in pH or ionic strength. The average molecular weight of the polyglutamic matrix used for porphyrin aggregate preparation plays a crucial role with regard to the form of the resulting CD spectrum. In the second part of our study, a complex composed of polylysine and bilirubin as a model system for a structured homoaggregate formed on the chiral matrix has been tested for chiral memory phenomena. The results indicate that the bilirubin homoaggregate shows chiral memory.     

Effect of para-Substituents on meso-Functionalized Oxidovanadium(IV) Porphyrins as Catalysts for Oxygen Atom Transfer Mediated Oxidation of Benzoin to Benzil under Mild Conditions

Systematic analysis of the effect of para-substituents (H, Cl, Br and OMe) on the meso-phenyl group in vanadyl meso-tetraphenylporphyrins ([V^IVO(TPP)] (R=H, 1 ), [V^IVO(TCPP)] (R=Cl, 2 ), [ V^IVO(TBPP)] (R=Br, 3 ) and [V^IVO(TMPP)] (R=OMe, 4 )) on their properties and catalytic oxygen atom transfer (OAT) for oxidation of benzoin to benzil using DMSO as well as 30 % aqueous H₂O₂ as the sacrificial oxygen source have been studied. Electrochemical and theoretical (density functional theory) studies are in good agreement with the influence of these substituents on the catalytic property of these complexes. Complex [V^IVO(TCPP)] ( 2 ) displayed the best catalytic activity for the conversion (92 %) of benzoin to benzil in 30 h with >99 % product selectivity when DMSO was used as an oxygen source, whereas excellent conversion (~100 %) of benzoin to benzil was noticed in 18 h with 95 % product selectivity when 30 % aqueous H₂O₂ was used as a source of oxygen. Furthermore, among these complexes, the electron-withdrawing nature of the chloro substituent at the p-position of meso-phenyl group significantly influences the oxygen atom transfer. Experimental and simulated EPR studies confirmed the +4 oxidation of vanadium in these complexes. The structure of 2 , 3 and 4 , confirmed by single crystal X-ray diffraction method, are domed in shape, and the displacement of V(IV) ion from the mean porphyrin plane follows the order: 2 (0.458 Å) < 3 (0.459 Å) < 4 (0.479 Å). We observed that the electron-withdrawing nature of chloro substituent at the p-position of meso-phenyl group influence the oxygen atom transfer from vanadyl porphyrin to dimethyl sulfide much.     

Porphyrin N-Pincer Pd(II)-Complexes in Water: A Base-Free and Nature-Inspired Protocol for the Oxidative Self-Coupling of Potassium Aryltrifluoroborates in Open-Air

Metalloporphyrins (and porphyrins) are well known as pigments of life in nature, since representatives of this group include chlorophylls (Mg-porphyrins) and heme (Fe-porphyrins). Hence, the construction of chemistry based on these substances can be based on the imitation of biological systems. Inspired by nature, in this article we present the preparation of five different porphyrin, meso-tetraphenylporphyrin (TPP), meso-tetra(p-anisyl)porphyrin (TpAP), tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (TSTpSPP), meso-tetra(m-hydroxyphenyl)porphyrin (TmHPP), and meso-tetra(m-carboxyphenyl)porphyrin (TmCPP) as well as their N-pincer Pd(II)-complexes such as Pd(II)-meso-tetraphenylporphyrin (PdTPP), Pd(II)-meso-tetra(p-anisyl)porphyrin (PdTpAP), Pd(II)-tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (PdTSTpSPP), Pd(II)-meso-tetra(m-hydroxyphenyl)porphyrin (PdTmHPP), and Pd(II)-meso-tetra(m-carboxyphenyl)porphyrin (PdTmCPP). These porphyrin N-pincer Pd(II)-complexes were studied and found to be effective in the base-free self-coupling reactions of potassium aryltrifluoroborates (PATFBs) in water at ambient conditions. The catalysts and the products (symmetrical biaryls) were characterized using their spectral data. The high yields of the biaryls, the bio-mimicking conditions, good substrate feasibility, evading the use of base, easy preparation and handling of catalysts, and the application of aqueous media, all make this protocol very attractive from a sustainability and cost-effective standpoint.