Thallium complexes of meso-tetra-(p-chlorophenyl)porphyrin: trifluoroacetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) and pentafluoropropionato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III)

The crystal structures of trifluoroacetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III), Tl[(p-Cl)₄tpp](O₂CCF₃) (1), and pentafluoropropionato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl[(p-Cl)₄tpp](O₂CCF₂CF₃) (2), were determined. The coordination sphere around the Tl³⁺ ion is described as five-coordinate regular square-based pyramid (RSBP) in which the apical site is occupied by an unidentate CF₃CO₂⁻ ligand for 1 whereas the unidentate CF₃CF₂CO₂⁻ ligand occupies the axial site for 2. The plane of the four pyrrole nitrogen atoms [i.e., N(1)–N(4)] strongly bonded to Tl³⁺ is adopted as a reference plane 4N. The Tl³⁺ is moderately out of the 4N plane; its displacement of 0.58 Å (or 0.59 Å) for 1 (or 2) is in the same direction as that of the trifluoroacetate oxygen for 1 (or pentafluoropropionate oxygen for 2). The free energy of activation at the coalescence temperature T_c for the intermolecular trifluoroacetate exchange for 1 in CD₂Cl₂ is found to be ΔG^≠₁₇₈=36.6 kJ/mol whereas the intermolecular pentafluoropropionate exchange for 2 in CD₂Cl₂ is determined to be ΔG^≠₂₁₃=41.5 kJ/mol through ¹⁹F and ¹³C NMR temperature-dependent measurements.     

中位-四(2,3,4,5,6-五氟苯基)卟啉锌合成方法的改进

中位－四（2,3,4,5,6－五氟苯基）卟啉锌的传统合成方法的转化率低、成本高、过程繁琐。通过对其合成方法中反应条件的改进,即以二甲苯代替2,6－二甲基吡啶,这样既降低了成本,又使后处理过程变得简单,且收率高于文献收率。     

水溶性meso-四(4-甲氧基-3-磺酸苯基)卟啉及其金属化合物合成新方法研究

采用浓硫酸和少量发烟硫酸在常温下合成了水溶性的四(4-甲氧基-3-磺酸基苯基)卟啉及其铁、钻、铜、锌、锰和镍金属化合物,采用核磁、质谱、紫外和元素分析仪对其结构进行了表征.该方法采用一定比例的浓硫酸和发烟硫酸混合物在常温下与卟啉反应,产物收率均超过98%.替代了文献中所采用的氯磺酸和硅烷氯磺酸酯等稳定性差且易于产生HC...     

新试剂meso－四（3－氯－4－磺基苯）卟啉光度法测定痕量钯的研究

研究了新试剂ｍｅｓｏ－四（３－氯－４－磺基苯）卟啉（ｍ－ＣｌＴＰＰＳ４）与钯的显色条件，建立了一种高灵敏光度法测钯的方法。在适当条件下，Ｐｄ（Ⅱ）与ｍ－ＣｌＴＰＰＳ４形成稳定的１∶１（Ｍ∶Ｌ）配合物，其最大吸收波长为４１４ｎｍ，表观摩尔吸光系数可达１．９×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。该方法应用于催化剂中痕量钯的测定。     

Aggregation of Tetrakis(4-methylpyridyl)porphyrin and tetrakis(4-sulphonatophenyl)porphyrin in water

The homo- and heteroaggregation of two oppositely charged water soluble porphyrins, tetrakis(4-methylpyridyl)porphyrin, TMPyP and tetrakis(4-sulphonatophenyl) porphyrin, TSPP has been studied by means of absorption and fluorescence spectroscopy in phosphate buffered saline. All experimental results on TSPP are consistent with a monomerdimer equilibrium (ΔH = −19.6 and ΔS = 19.3 kJ mole⁻¹). The absorption spectrum of the TSPP dimer was obtained from a global fit of a set of spectra to the monomer dimer model. TMPyP does not aggregate at concentrations up to 10⁻⁴M . Changes in the fluorescence spectrum of TMPyP upon dilution are due to adsorption phenomena. 1:1 heteroagregates of both porphyrins cannot be characterized in water solution due to extreme small solubility. A 2:1 heteroaggregate is detectable in solution. It is proposed to exploit the extreme small solubility of heteroaggregated oppositely charged porphyrins to increase the selective retention of porphyrins provided there is an initial selectivity of ether component.     

四(4-磺酸苯基)卟啉的微波合成

用微波辐射加热合成了四(4-磺酸苯基)卟啉。考察了微波作用的时间、微波辐射功率、反应试剂的组成与用量等因素对产物产率的影响。     

卟啉及其衍生物的合成研究进展

按卟啉母核的不同合成方法,介绍了从各种小分子的缩合而合成卟琳的方法包括经典的Alder-Long法、Lindsey法和新颖的[2 2]法、[3 1]法、线形四吡咯出发合成卟啉、2_位取代吡咯合成卟啉,这些方法能够合成许多不同结构的卟啉化合物.     

新试剂meso─四（3─溴─4─羟基─5─甲氧基苯基）卟啉的合成及其性质的研究

报道了新试剂ｍｅｓｏ－四（３－溴－４－羟基－５－甲氧基苯基）卟啉的合成方法，对试剂的理化性质、分析特性及其与金属离子的显色反应也作了研究，并提出了该试剂的应用前景。     

氯化四-(对氯苯基)铁卟啉催化氧化邻硝基甲苯的表观动力学研究

研究了氯化四-(对氯苯基)铁卟啉T(p-Cl)PPFeCl催化氧化邻硝基甲苯的表观动力学.在确定邻硝基苯甲醛和邻硝基苯甲酸为主要产物的基础上,建立了连串反应模型和速度方程.根据不同温度条件下所测得的反应速率常数,确立了邻硝基甲苯氧化生成邻硝基苯甲醛的第一步反应为一级反应,且表观活化能为99.5 kJ/mol;而邻硝基苯甲醛氧化生成邻硝基苯甲酸的第二步反应为1/2级反应,且表观活化能为82.9 kJ/mol.通过比较两步反应的表观活化能和反应速率常数,发现升高温度有利于邻硝基苯甲醛的生成,且反应速率较快.     

meso-四-(4-辛氧基-3-甲氧基苯基)卟啉及其金属配合物的合成与表征

报道了一种新型对称型卟啉化合物meso-四-(4-辛氧基-3-甲氧基苯基)卟啉(TOMPPPH2)及其金属钌、钯配合物(Ru(DMF)2TOMPPP,PdTOMPPP)的合成,并通过可见光谱,红外光谱,核磁共振氢谱和元素分析等对这些卟啉化合物的结构进行了表征。     

4-烷基苯甲酸液晶中间体的合成及其液晶性能

以苯、C2～C5的酰氯为原料,经傅-克酰基化、黄鸣龙还原、乙酰化反应和溴仿反应合成了4个端基为C2～C5的单环芳香酸。以气相色谱-质谱联用仪、红外光谱仪、紫外光谱仪对芳香酸结构进行了表征。利用差热扫描量热仪、热台偏光显微镜对化合物的液晶性能进行了测试。结果表明,对于分子的长径比小于4的这类化合物,通过分子间氢键缔合的形式,亦可产生液晶相;其液晶相温度范围为9～20℃,呈现出向列相纹影织构。     

meso-四(4-N-乙基吡啶基)金属卟啉催化剂的合成及其催化活性的表征

采用两条路线合成了季铵阳离子型的meso-四(4-N-乙基吡啶基)卟啉和对应的铁、钴,铜,锌,锰等几种金属配合物催化剂,采用UV-Vis、IR、MS和EA等对其结构进行了表征.同时,采用碱性甲醇溶液中氧气氧化对硝基甲苯制备对硝基苯甲酸作为模型反应,对上述催化剂的催化性能进行了表征,发现这些催化剂均有显著的活性.其中溴化...     

The synthesis,spectroscopy, electrochemistry and photophysical properties of novel,sandwich europium(III) complexes with a porphyrin ligand bearing four pyrenyl groups in meso-positions

Novel, metal free porphyrins containing four pyrenyl groups in the meso-positions were used to provide novel, sandwich-type mixed tetrapyrrole europium double- and triple-deck complexes. The sandwich-type complexes together with the metal free porphyrin were characterized using electronic absorption, IR and ¹H NMR spectroscopy in addition to elemental analysis. The electrochemical behaviour of the sandwich complexes was investigated by cyclic voltammetry and differential pulse voltammetry in CH₂Cl₂, their photophysical properties were studied in comparison to those of the metal free porphyrin ligand. Fluorescence quenching observed was tentatively attributed to efficient and rapid energy transfer from the pyrenyl groups to porphyrin followed by electron transfer from porphyrin to phthalocyanine.     

Optical and electro-optical properties of (CH3)4NHgBrI2 crystals

(CH₃)NH_gBrI₂ is an electro-optic material which shows a structural phase transition with a symmetry change from orthorhombic to monoclinic at T = 108°C upon heating. In this contribution we report first experimental data on the optical properties (refractive indices, absorption coefficients), on the elastic and electro-optical properties. It is shown, that the dispersion of the refractive indices is adequately described by a single term Sellmeier oscillator model. Measurements of the temperature dependence of the birefringence and of the elastic constants show pronounced changes at the structural phase transition. The biaxial crystal with the three main indices n_a = 1.761±0.001, n_b = 1.802±0.001 and n_c = 1.755±0.001 at room temperature and a wavelength λ=633nm becomes optically uniaxial at T = (50±0.5)°C with n_a=n_c=1.750, due to different temperature dependences n_a(T) and n_b(T). Room temperature electro-optic coefficients and the corresponding half-wave voltages have been determined, and indicate that the electro-optic activity of (CH₃)₄NH_gBrI₂ is about two orders of magnitude smaller than in KH₂PO₄.     

Zn(Pro) 2-promoted CuI-catalyzed synthesis of diphenyl sulfide derivations in ionic liquid

We report a mild, palladium-free synthetic protocol for the cross-coupling reaction of aryl chlorides and thiols under the assistance of Zn complexes of proline and CuI, with K₂CO₃ as the base, performed at 110 °C in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF ₄). This protocol is particularly noteworthy given its experimental simplicity, high generality, and the exceptional level of functional group tolerations and low cost of the catalyst system.     

The preparation and properties of zinc coordination complexes of poly(4-vinylpyridine-co-n-butyl methacrylate) copolymers

Two poly(4-vinylpyridine-co-n-butyl methacrylate) copolymers containing 14.2 and 30.0 mol% of 4-vinylpyridine residues were prepared by free radical copolymerization reactions. Insoluble complexes were obtained for each copolymer by reaction with zinc chloride. The coordination complexes obtained had a molar ratio of 4-vinylpyridine residues to zinc atoms close to 2 in both cases. The rheological behavior of each of these complexes has been compared to that of the corresponding metal-free copolymers, which were recovered by decomplexation. The metal complexed polymers exhibited much higher glass transition temperatures and much longer high temperature relaxation times than the corresponding uncomplexed copolymers.     

Molecular recognition of amines by a chiral Zn(II) porphyrin complex

Equilibria of the reactions of a Zn(II) `picket-fence' porphyrin complex bearing optically active substituents with chiral amines were studied. Stability constants were determined by spectrophotometric titration in dichloromethane solution. Chiral recognition in the complexation of amine to the α,β,α,β-isomer of the complex was observed for 1-(1-naphthyl)ethylamine with the ratio of the binding constant of K_S/K_R=2.4.     

Zn2 +-assisted synthesis of concave Cu2O crystals and enhanced photocatalytic properties

The effects of Zn^2 + on the structure Cu₂O crystals and photocatalytic decoloration of methylene orange (MO) were studied. Samples were characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), and Ultraviolet–Visible Spectroscopic (UV–VIS). The results indicated that Zn^2 + ions can transform the surface curvature of Cu₂O microcrystals from convex to concave. Tests of photodecoloration showed that the concave trisoctahedron Cu₂O microcrystals exhibited higher catalytic activity than those of octahedra Cu₂O and convex Cu₂O for MO under visible light.     

Pyrazolyl-diamine ligands that bear anthracenyl moieties and their rhenium(I) tricarbonyl complexes: synthesis, characterisation and DNA-binding properties

Two novel families of pyrazolyl-diamine ligands that bear an anthracen-9-yl group as a DNA-binding fragment, pz*(CH2)2NH(CH2)2NHCH2-9-anthryl (pz*=pz (L(1)), 3,5-Me2pz (L2)) and pz*(CH2)2NH(CH2)2NH(2 (pz*=4-(9-anthrylmethyl)pz (L3), 3,5-Me2-4-(9-anthrylmethyl)pz (L4)), have been prepared and fully characterised. In the case of L2-L4, the evaluation of their coordination capability towards the fac-[Re(CO)3]+ core led to the synthesis of the organometallic complexes fac-[Re(CO)(3){3,5-Me(2)pz(CH2)2NH(CH2)2NHCH2-9-anthryl}]Br (7) and fac-[Re(CO)3{4-(9-anthrylmethyl)pz*(CH2)2NH(CH2)2NH2}]Br (pz*=pz (8), 3,5-Me2pz 9). The interaction of the novel pyrazole-diamine ligands and the rhenium(I) complexes with calf thymus (CT) DNA has been investigated with a variety of spectroscopic techniques (UV-visible, fluorescence, circular dichroism (CD) and linear dichroism (LD)). All of the evaluated compounds have a moderate affinity to CT DNA (3.46x10(3)相似文献