聚合物键联钴卟啉的合成及其催化作用

合成了 5 -对羟苯基 - 1 0 ,1 5 ,2 0 -三 (对甲氧苯基 )卟啉 (1 )及其钴配合物 (2 )。将(1 )与氯甲基化聚苯乙烯树脂键合得聚合物键联卟啉 (3) ,(3)与钴离子络合得聚合物键联钴卟啉 (4) ,考察了 (4)对丙硫醇的催化氧化作用。对卟啉化合物进行了 IR、UV测定和元素分析。对丙硫醇氧化产物作了 HPL C、UV、IR和 MS分析。     

Polyimides from a Novel Monomer 3,6-Bis(dimethylamino)acridine(p-cymene)dichlororuthenium(II) for a Catalytic Application

Tricyclic heteroaraomatic dye-based monomer containing NMe₂ units, 6-bis(dimethylamino)acridine(p-cymene)dichlororuthenium (II), was used to prepare novel polyimides via a one-stage solution polycondensation due to their stability under a variety of oxidative and reductive conditions. The Ru(II) complex monomer was synthesized starting from [RuCl₂(p-cymene)]₂ and 3,6-bis(dimethylamino)acridine. A series of stable polyimides was synthesized from the Ru(II) complex of 3,6-bis(dimethylamino)acridine and various aromatic dianhyrides. The polymers had inherent viscosities ranging from 1.72 to 2.11 dL/g and were soluble in polar solvents. The glass transition temperatures were 192–278 °C, and the 10% weight loss temperatures were above 503–635 °C. Ruthenium-substituted polyimides were tested for catalytic activity in the furan formation reaction of (Z)-3-methylpent-2-en-4-yn-1-ol. The polymeric catalyst was added to (Z)-3-methylpent-2-en-4-yn-l-ol without a solvent and the pure furan was isolated by distillation under reduced pressure. The conversion of the starting, enynol, was determined by gas chromatography (GC).     

Polyimides from a Novel Monomer 3,6-Bis(dimethylamino)acridine(p-cymene)dichlororuthenium(II) for a Catalytic Application

Tricyclic heteroaraomatic dye-based monomer containing NMe₂ units, 6-bis(dimethylamino)acridine(p-cymene)dichlororuthenium (II), was used to prepare novel polyimides via a one-stage solution polycondensation due to their stability under a variety of oxidative and reductive conditions. The Ru(II) complex monomer was synthesized starting from [RuCl₂(p-cymene)]₂ and 3,6-bis(dimethylamino)acridine. A series of stable polyimides was synthesized from the Ru(II) complex of 3,6-bis(dimethylamino)acridine and various aromatic dianhyrides. The polymers had inherent viscosities ranging from 1.72 to 2.11 dL/g and were soluble in polar solvents. The glass transition temperatures were 192–278 °C, and the 10% weight loss temperatures were above 503–635 °C. Ruthenium-substituted polyimides were tested for catalytic activity in the furan formation reaction of (Z)-3-methylpent-2-en-4-yn-1-ol. The polymeric catalyst was added to (Z)-3-methylpent-2-en-4-yn-l-ol without a solvent and the pure furan was isolated by distillation under reduced pressure. The conversion of the starting, enynol, was determined by gas chromatography (GC).     

Synthesis,structures and properties of a meso-substituted pyrazolyl porphyrin and its Co(II) porphyrin complex

In this work, one new porphyrin, 5, 10, 15, 20-tetrakis(4-N-pyrazolyl)phenyl porphyrin (H₂Pp) was synthesized and characterized. The single crystal structures of H₂Pp and its cobalt(II) porphyrin (Co(II)Pp) were obtained with a space group of P₁⁻ and I2/c, respectively. The porphyrin macrocycle is close to a perfect plane in H₂Pp, while Co(II)Pp exhibits a saddle-type distortion due to the formation of shorter Co–N coordination bonds. In H₂Pp, the molecules are interconnected through π⋯π and C–H⋯π interactions to form 3D architecture, while in Co(II)Pp the porphyrin molecules are interlinked only by C–H⋯π interactions to yield 3D structure. We examined the UV–vis spectra and fluorescent spectra of H₂Pp and Co(II)Pp in CH₂Cl₂ and solid state at room temperature. In addition, the catalytic activities of Co(II)Pp to the ethylbenzene oxidation was examined, the results indicate that Co(II)Pp exhibits a high selectivity to acetophenone (> 99%) with the conversion of 83%.     

新型钯配合物合成及其光催化降解有机染料研究

近年来,有机钯配合物被发现具有优异的催化性能因而被广泛应用于催化反应。一种新型钯配合物[Pd(L)(Cl)2]已经通过常温挥发法合成出来(其中L代表1,3-双(二苯基膦基)丙烷配体),并通过元素分析,红外光谱和X射线单晶衍射仪进行了表征。在这个钯配合物中,氢键在结构组成中起到了很重要的作用。研究表明,该钯配合物具有良好的光催化降解有机染料活性。     

Synthesis of a new iron (III) porphyrin acrylate-styrene copolymer and its catalysis for hydroxylation of cyclohexane

A new iron (III) porphyrin acrylate-styrene copolymer, P[(PorFe)A-S], was synthesized by the reaction of iron (III) porphyrin acrylate with styrene and characterized by UV-Vis, Infrared spectra (IR), inductively coupled plasma-atomic emission spectrometry (ICP) and molecular weight determination. Its catalytic activity in the hydroxylation of cyclohexane for model cytochrome P450 in the P[(PorFe)A-S]-O₂ ascrobate-thiosalicylic acid system has been studied. It was found that the P[(PorFe)A-S] has a higher catalytic activity than non-supported iron (III) porphyrin and its high catalytic activity remained in reuse. The catalytic activity of P[(PorFe)A-S] was discussed in the view of the microenvironment of iron (III) porphyrin. It is proposed that the atalytic activity of the P[(PorFe)A-S] may be further enhanced by construction of a homophase catalytic system containing the iron (III) porphyrin acrylate-styrene copolymer.     

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     

New antimicrobial agents: The synthesis of Schiff base polymers containing transition metals and their characterization and applications

A new polymeric Schiff base containing formaldehyde and 2‐thiobarbituric acid moieties was synthesized by the condensation of a monomeric Schiff base derived from 2‐hydroxyacetophenone and hydrazine. Polymer–metal complexes were also synthesized by the reaction of the polymeric Schiff base with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) acetate. The polymeric Schiff base and its polymer–metal complexes were characterized with magnetic moment measurements, elemental analyses, and spectral techniques (infrared, ¹H‐NMR, and ultraviolet–visible). The thermal behaviors of these coordination polymers were studied by thermogravimetric analysis in a nitrogen atmosphere up to 800°C. The thermal data revealed that all of the polymer–metal complexes showed higher thermal stabilities than the polymeric Schiff base and also ascribed that the Cu(II) polymer–metal complex showed better heat resistant properties than the other polymer–metal complexes. The antimicrobial activity was screened with the agar well diffusion method against various selected microorganisms, and all of the polymer–metal complexes showed good antimicrobial activity. Among all of the complexes, the antimicrobial activity of the Cu(II) polymer–metal complex showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

ESR studies on the dimer formation between copper ions in the poly(vinylimidazole) · copper(II) complex

Summary ESR studies were made on the poly (vinylimidazole)· copper(II) complex in a lower magnetic field near 1600 gauss. The absorption in this region was observed for the poly(vinylimidazole) · copper (II) complex system while no absorption was present for the imidazole· copper (II) complex. The result was interpreted in terms of the dipolar interaction between copper (II) ions in the polymeric complex system, where the copper (II) ions were put together on the polymeric ligand in a highly condensed state.     

Synthesis of a new iron(III) porphyrin acrylate-styrene copolymer and its catalysis for hydroxylation of cyclohexane

A new iron(III) porphyrin acrylate-styrene copolymer, P[(PorFe)A-S], was synthesized by the reaction of iron(III) porphyrin acrylate with styrene and characterized by UV-Vis, Infrared spectra (IR), inductively coupled plasmaatomic emission spectrometry (ICP) and molecular weight determination. Its catalytic activity in the hydroxylation of cyclohexane for model cytochrome P450 in the P[(PorFe) A-S]-O₂-ascrobate-thiosalicylic acid system has been studied. It was found that the P[(PorFe)A-S] has a higher catalytic activity than non-supported iron(III) porphyrin and its high catalytic activity remained in reuse. The catalytic activity of P[(PorFe)A-S] was discussed in the view of the microenvironment of iron(III) porphyrin. It is proposed that the catalytic activity of the P[(PorFe)A-S] may be further enhanced by construction of a homophase catalytic system containing the iron(III) porphyrin acrylate-styrene copolymer. Translated from Acta Scientiarum Naturalium Universitatis Sunyatseni, 2006, 45(1): 61–63 [译自: 中山大学学报 (自然科学版)]     

Synthesis and characterization of fully conjugated porphyrin tapes

meso-meso, ß-ß, ß-ß Triply-linked zinc(II) porphyrin tapes were synthesized by powerful oxidation of meso-meso-linked zinc(II) porphyrin arrays up to tetramers with DDQ-Sc(OTf)₃. Coordination of butylamine to zinc(II) ions of porphyrin rings dissociates their aggregation, resulting in clear NMR spectra and sharper red-shifted absorption bands.     

5-(4'-羟基苯基)-10,15,20-三(4'-三甲硅基苯基)卟啉的合成

以4-羟基苯甲醛、4-三甲硅基苯甲醛、吡咯(物质的量比1∶3∶4)为原料,借鉴Lindsey方法合成了5-(4'-羟基苯基)-10,15,20-三(4'-三甲硅基苯基)卟啉。研究了提纯该化合物的手段,最终得到了分离效果好的分离方法。其结构由1HNMR、质谱、紫外等表征。     

Polymeric Salphen‐phthalocyanine dinuclear metal complexes for activation of molecular oxygen

The polymeric Salphen Schiff base‐phthalocyanine Co‐Cu dinuclear metal complex (PSalphenCo‐PcCu) was designed and synthesized through interfacial condensation polymerization. The new sheet polymeric dinuclear metal complex has been characterized by IR spectra, UV‐visible spectra, scanning electron microscopy with energy dispersive X‐ray analysis and thermogravimetry analysis. Its catalytic activity for activation of molecular oxygen was investigated by using cumene as substrate without any additive in mild condition. The aerobic oxidation of cumene catalyzed by PSalphenCo‐PcCu proved to be a simple and efficient method for obtaining cumene hydroperoxide in a high selectivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

不同金属卟啉光催化降解亚甲基蓝性能研究

以四苯基卟啉(TPP)为原料,通过金属插入反应,获得FeTPP、ZnTPP、CoTPP、MnTPP,并用UV-Vis对其进行了表征.将合成的金属卟啉用于光催化体系,进行亚甲基蓝溶液的光催化降解及催化剂回收实验.结果发现,以CoTPP为催化剂,在高压汞灯光照3 h后,亚甲基蓝溶液的脱色率可迭100%;不同光源的催化效果为...     

手性麻黄素-卟啉锰催化剂的合成及催化性能的研究

以一类新型的手性麻黄素 -卟啉作配体 ,制备了金属锰配合物。考察了配合物对烯烃环氧化反应的催化性能 ,发现含麻黄素基团的锰卟啉催化剂在烯烃环氧化的两相溶剂 ( CH2 Cl2 /H2 O)体系中 ,不仅催化活性增强 ,同时具有相转移能力。还探讨了反应条件对环氧化结果的影响规律     

Metalloporphyrin/Iodine(III)‐Cocatalyzed Oxygenation of Aromatic Hydrocarbons

Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrin‐mediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5–20 mol% of iodobenzene and 5 mol% of a water‐soluble iron(III)‐porphyrin complex. 2‐tert‐Butylanthracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10‐dihydroanthracene, 1,2,3,4‐tetrahydronaphthalene, and 2,3‐dihydro‐1H‐indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)‐porphyrin to the oxoiron(IV)‐porphyrin cation‐radical complex by the intermediate iodine(III) species. The oxoiron(IV)‐porphyrin cation‐radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.     

Synthesis of a porphyrinic polymer for highly efficient oxidation of arylalkanes in water

A highly stable covalent-porphyrinic framework Mn-CPF-1 was synthesized by reaction of cyanuric chloride and tetraphenylamine porphyrin (TAPP) and subsequent metallation. Mn-CPF-1 exhibits remarkable catalytic activity and stability on catalytic oxidation of arylalkanes in water under mild conditions, which is much superior to the homogeneous analog Mn-tetraphenylporphyrin (Mn-TPP) under identical conditions.     

Selective molecular oxygen transport through a cellulose acetate membrane containing an electron-poor iron(II) porphyrin complexes

Molecular oxygen diffusion in the cellulose acetate membranes containing the 5,10,15, 20-tetrakis(pentafluorophenyl)-21H,23H-porphine iron(II) was studied. Both the permeability coefficient and the separation factor for oxygen in the membrane containing the iron(II) porphyrin complex were increased with decreasing the upstream gas pressure which correspond to a dual-mode oxygen transport. The effects of the axial ligands of the iron(II) porphyrin on oxygen permeation was also examined in the same cellulose acetate membrane. The fluoride and 2-methyl imidazole ligands coordination to the iron(II) porphyrin induce to increase the oxygen permeability coefficient and the value of ideal separation factor.     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004