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     

四(4-硝基苯基)卟啉和四(4-氨基苯基)卟啉的合成

四（４氨基苯基）卟啉（ＴＡＰＰ）是含有４个反应活性基团的卟啉衍生物,可在模拟某些生物过程或氧化还原反应的树枝状或簇状分子中作为富电子中心,也可直接用来制备光电器件或作为光电功能聚合物的功能单体和交联剂,因此,ＴＡＰＰ的合成研究具有重要意义［１］．...     

5,10,15,20-四(4-(4-吡啶)酮基)苯基卟啉的合成、表征及晶体结构

利用丙酸法合成了一种新的化合物5,10,15,20-四(4-(4-吡啶)酮基)苯基卟啉,并进行了IR,UV-Vis,MS及EA表征,探讨了试剂4-羟基吡啶的异构现象及合成方法。采用溶液结晶法得到了该卟啉分子的晶体,对其进行了X-射线单晶衍射及粉末衍射测定。结果表明:该晶体属于正交晶系,空间群为Fddd。相邻的卟啉分子通过吡啶环之间的π…π作用与其他卟啉分子相连形成二维层状结构。层与层之间进一步通过吡啶环与卟啉环之间的π…π作用而形成三维超分子结构。该化合物可以作为构建金属卟啉框架新材料(MPF)的良好配体。     

卟啉环上的亲核取代：2-(2-萘酚)-5,10,15,20-四苯基卟啉的合成

为了制备2-取代卟啉，研究了2-硝基-5,10,15,20-四苯基卟啉1及其镍2，铜3，锌4配合物与2-萘酚钠在不同溶剂中的反应。在2-萘酚中，150℃的温度下反应，分别得到2-(2-萘酚)-5,10,15,20-四苯基卟啉5 （72%）, 及其镍(II) 6（78%）, 铜(II) 7（81%）, 锌(II) 8（65%）配合物。在其它质子性溶剂如一缩二乙二醇和一缩二乙二醇单甲醚中反应，得到相同的产物。当在非质子性溶剂DMF，150 ℃的温度下反应，除了得到5 (70%)，6 (34%)，7 (54%), 8 (50%)外，还分别得到微量2-(2-萘氧基)-5,10,15,20-四苯基卟啉9, 及其镍(II) 10（40%）,铜(II) 11（18%）, 锌(II)12 （2%）配合物。但室温下，无论用DMF还是DMSO做溶剂，均只得到5，6，7，8。卟啉1-4与萘酚钠的反应比与苯酚钠反应快，C-C键产物5-8的形成被认为是通过S_RN1机理进行的。     

meso-四(2-羟基-5-磺酸苯基)卟啉的合成及其酸碱平衡的研究

本文对 meso-四(2-H-5-SP)P 的提纯方法进行了改进,同时以光度法研究了该试剂在水溶液中的酸碱平衡、测得其 pKa_1、pKa_2、pKa_3、pKa_4分别为2.99,4.21,8.68,10.28。     

2-(2-氨基苯基)苯并噻唑与四苯基卟啉及四苯基锌卟啉的荧光共振能量转移

采用紫外光谱和荧光光谱法研究了四氢呋喃溶液中2-(2-氨基苯基)苯并噻唑(APBT)与四苯基卟啉(TPP)、四苯基锌卟啉(ZnTPP)之间的相互作用.结果表明,APBT可作为能量供体分子分别与能量受体分子TPP或ZnTPP构成荧光共振能量转移(FRET)体系,APBT的作用将使TPP和ZnTPP的荧光增强.在此FRET...     

从2-硝基卟啉和氢醌直接合成β-氢醌卟啉及其氢醌卟啉的分子识别研究

首次利用对苯二酚与 2 硝基卟啉 ( 1)及其金属配合物直接反应 ,合成了 2 氢醌取代卟啉及其相应金属配合物 :2 ( 2 ,5 二羟基苯基 ) 5 ,10 ,15 ,2 0 四苯基卟啉 ( 5 ) ( 81%) ,2 ( 2 ,5 二羟基苯基 ) 5 ,10 ,15 ,2 0 四苯基卟啉镍 (II) ( 6) ( 61%) ,2 ( 2 ,5 二羟基苯基 ) 5 ,10 ,15 ,2 0 四苯基卟啉铜 (II) ( 7) ( 71%) ,2 ( 2 ,5 二羟基苯基 ) 5 ,10 ,15 ,2 0 四苯基卟啉锌 (II) ( 8) ( 4 1%) ,并利用UV vis、荧光光谱、电化学等方法 ,研究了 2 硝基卟啉 1和 2 氢醌卟啉 5对多种苯醌类衍生物的分子识别 .实验表明5对醌具有较好的识别能力 .     

氧化锌负载四(4-硝基苯基)钴卟啉催化氧化环己烷性能

将四(4-硝基苯基)钴卟啉(Co-TNPP)负载在氧化锌(Zn O)载体制备负载型金属卟啉催化剂Co-TNPP/Zn O,并对其进行了紫外-可见漫反射光谱(UV-vis),红外光谱(FT-IR),X射线衍射(XRD),热重分析(TG/DTG),比表面分析(BET)和电感耦合等离子体(ICP)表征.考察了催化剂在无溶剂的条件下催化氧气氧化环己烷的性能.实验结果表明:在反应温度为150℃,氧气压力为1.2 MPa,反应时间为2.0 h的条件下,环己烷转化率9.82%,环己醇和环己酮选择性83.37%.负载型金属卟啉催化剂经过5次循环使用,环己烷的平均转化率和环己醇、环己酮平均选择性分别为9.95%、83.61%,催化剂的平均转化数为2.18×105.负载型金属卟啉催化剂Co-TNPP/Zn O在较温和的条件下表现出优良的环己烷催化氧化性能,克服了金属卟啉催化剂难以回收、无法循环使用的缺点,具有很好的工业价值和应用前景.     

5,10,15,20-四(对-癸酰氧基苯基)卟啉过渡金属配合物的合成与表征

液晶;5;10;15;20-四(对-癸酰氧基苯基)卟啉过渡金属配合物的合成与表征     

三(4-硝基苯基)甲醇及其氯化物的合成与表征

以三苯甲烷为原料,经硝化、氧化和氯化三步反应合成了三(4-硝基苯基)甲烷(TNPM),三(4-硝基苯基)甲醇(TNPMO)和三(4-硝基苯基)氯甲烷(TNPMCl)等一系列三芳基甲烷类化合物.三苯甲烷经混酸硝化制备TNPM;然后经CrO3/冰醋酸氧化生成TNPMO,最后与乙酰氯反应得到TNPMCl.各步产物的结构经核磁共振与红外光谱进行了表征.     

Synthesis and properties of 5,10,15,20-tetra(4-lauroylimidophenyl)porphyrin and its metal complexes

Transition metal complexes of 5,10,15,20-tetra(4-lauroylimidophenyl)porphyrin TLPPM [M = Mn(Cl), Fe(Cl), Co, Ni, Cu, Zn] have been synthesized and characterized by means of elemental analyses, UV–VIS spectra, infrared spectra, ¹H NMR spectra, molar conductance, differential scanning calorimetry (DSC), polarized optical microscopy (POM), cyclic voltammetry, luminescence spectra and surface photovoltage spectroscopies. The porphyrin ligand shows liquid crystalline behaviour, and it exhibits a high phase transition temperature 182 °C and a broad mesophase temperature span, 88 °C. The oxidation and reduction properties of the compounds were investigated by cyclic voltammetry. The photovoltaic properties and charge transfer process of the compounds were investigated by surface photovoltage spectroscopy (SPS) and electric field-induced surface photovoltage spectroscopic (EFISPS) techniques, which revealed that all the compounds are p-type semiconductors. Quantum yields of the S₁ → S₀ fluorescence were measured at room temperature. These studies will contribute to further choice and application of the liquid crystals.     

Electrochemical synthesis and properties of polyporphyrin films based on 5,10,15,20-tetra(4-pyridyl)porphyrin

Polyporphyrin films were obtained by electrooxidative polymerization of 5,10,15,20-tetra(4-pyridyl)porphyrin which, in turn, was obtained by condensation of pyrrole with pyridine-4-carboxaldehyde. The polymer formation involved the side substituents, with the π-conjugated porphyrin platform being preserved. The obtained polyporphyrin forms an electroconductive coating possessing semiconductor properties with the band gap of 1.76 eV     

Photophysical properties of carborane-containing derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin

Absorption, fluorescence emission, fluorescence excitation spectra and fluorescence decay kinetics of carborane derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin have been investigated. Carborane derivatives are prepared by acylation of the amino groups of 5,10,15,20-tetra(p-aminophenyl)porphyrin by 9-carboranyl acetyl chloride. From the analysis of the absorption and fluorescence spectra, it is concluded that covalent linking of carborane molecules to the tetraphenylporphyrin molecule significantly changes the self-conjugated pi-system of the porphyrin macrocycle: positions of maxima of absorption and fluorescence spectra shift to the red region by 3-8 nm; the halfwidths of these bands are broadened by 2.5-5.0 nm; the relative intensity of the bands I-IV also changes. The fluorescence decay kinetics of the carborane derivatives are biexponential. According to the experimental data and model simulation, it is concluded that the intramolecular electron transfer proceeds from the porphyrin excited part of the molecule to carboranyls with a rate constant of 415 ps(-1) and efficiency of 0.16-0.8. Recombination of separated charges occurs within 1.4 ns.     

meso－5，10，15，20－四（3，4，5－三甲氧基苯基）卟啉的晶体和分子结构

用Ｘ－射线测定了ｍｅｓｏ－５，１０，１５，２０－四（３，４，５－三甲氧基苯基）卟啉的溶剂（正庚烷）合物（ＴＴＯＭＰＰ·２Ｃ＿７Ｈ＿（１６））的晶体结构。实验表明，该化合物（Ｃ＿（７０）Ｈ＿（８６）Ｎ＿４Ｏ＿（１２））的晶体属三斜晶系，空间群Ｐ１，ａ＝８．７４９（６），ｂ＝１５．１２９（６），ｃ＝１６．４４９（３），ａ＝６０．０７（３），β＝７０．６４（４），γ＝８１．７０（５），Ｖ＝１７７９．６，Ｍ＿ｒ＝１１７５．４９，Ｚ＝１，Ｄ＿ｃ＝１．０９７ｇ／ｃｍ￣３，μ＝０．６９７ｃｍ￣（－１），Ｆ（０００）＝６３０。讨论了卟啉环上取代基的电子和立体效应及卟啉与铁（Ⅲ）离子配位后铁（Ⅲ）离于对卟啉结构参数的影响。     

meso－5，10，15，20－四（3，4，5－三甲氧基苯基）卟啉的晶体和分子结构

用Ｘ－射线测定了ｍｅｓｏ－５，１０，１５，２０－四（３，４，５－三甲氧基苯基）卟啉的溶剂（正庚烷）合物（ＴＴＯＭＰＰ·２Ｃ＿７Ｈ＿（１６））的晶体结构。实验表明，该化合物（Ｃ＿（７０）Ｈ＿（８６）Ｎ＿４Ｏ＿（１２））的晶体属三斜晶系，空间群Ｐ１，ａ＝８．７４９（６），ｂ＝１５．１２９（６），ｃ＝１６．４４９（３），ａ＝６０．０７（３），β＝７０．６４（４），γ＝８１．７０（５），Ｖ＝１７７９．６，Ｍ＿ｒ＝１１７５．４９，Ｚ＝１，Ｄ＿ｃ＝１．０９７ｇ／ｃｍ￣３，μ＝０．６９７ｃｍ￣（－１），Ｆ（０００）＝６３０。讨论了卟啉环上取代基的电子和立体效应及卟啉与铁（Ⅲ）离子配位后铁（Ⅲ）离于对卟啉结构参数的影响。     

Synthesis of 5,10,15,20-tetra[6' -nitro-1,3,3-trimethylspiro- (indolino-2,2' -2H-chromen-5-yl)]porphyrin and its metal complexes

A new 5,10,15,20-tetrasubstituted porphyrin containing four 6’-nitro-1,3,3-trimethylspiro(indolino-2,2’-2H-chromene) substituents and its complexes with Zn²⁺ and Cu²⁺ ions were prepared and characterized by physicochemical methods of analysis.     

The interaction of 2-hydroquinone-5,10,15,20-tetra(p-hydroxyphenyl)porphyrin with surfactants: solubilization and J-aggregates

J-aggregates of 2-hydroquinone-5,10,15,20-tetra(p-hydroxyphenyl)porphyrin (HQTHPP) induced by N-lauroyl sarcosine (SKL) in aqueous neutral solutions have been studied by optical absorption, fluorescence, and resonance light-scattering spectroscopies. As SKL concentration increases, the spectra evolve to reveal the presence of four independent species with relative concentration. The most important species is J-aggregates. The J-aggregates have two strong exciton bands corresponding to the B-band and Q-bands of HQTHPP monomers, and are found to be stable when the surfactant concentration is below 8.0 mmol/L. But above 8.0 mmol/L, the J-aggregates dissolve gradually into another species: porphyrin monomers. The total fluorescence of HQTHPP is quenched due to the aggregate formation. A strong and sharply peaked resonance light-scattering signal (>1800 counts/s, centered at 490 nm) is observed just slightly to the red of the J-aggregate absorption maximum. In the case of cetyltrimethyl-ammonium bromide, increasing surfactant concentrations have only shown to favor solubilization of porphyrin monomers. Evidently, the nature of polar headgroups of surfactants influences the tendency of THPP to aggregate.     

Chelation and fluorescence properties of tetraphenylporphyrin and 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin in acetonitrile

The kinetics of complex formation between zinc and 5,10,15,20-tetraphenylporphyrin and 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin in acetonitrile is studied in the temperature range from 298 to 318 K. The fluorescent properties of these compounds are examined, the emission in the red region of the spectrum is measured, and the fluorescence quantum yields are determined. It is found that although the electronic absorption spectra of the studied compounds are almost identical, hydroxyl substituents are observed to have a considerable effect on the chelating ability of ligands. The rate constant of the formation of ZnT(4-OH-Ph)P is thus approximately three times higher than that of ZnTPhP, with the energy consumption being lower (about 20 kJ mol^–1). The calculated fluorescence quantum yields of H₂TPhP, H₂T(4-OH-Ph) P, ZnTPhP, and ZnT(4-OH-Ph)P in acetonitrile are half those in toluene, while the ratio between the quantum yields of ligands and their metal complexes is a constant equal to approximately 3 and does not depend on which solvent is used.     

Synthesis and characterization of 5,10,15,20-tetra[3-(3-trifluoromethyl)phenoxy] porphyrin

The newly synthesized 5,10,15,20-tetra[3-(3-trifluoromethyl)phenoxy]porphyrin, TTFMPP, has been characterized using mass spectroscopy, 1H-, 13C- and 19F-NMR, MALDI-TOF mass spectrometry, UV-Vis and fluorescence spectrophotometry, and cyclic voltammetry. The NMR confirmed the structure of the compound and the mass spectrum was in agreement with the proposed molecular formula. The UV-Vis absorption spectrum of TTFMPP shows characteristic spectral patterns similar to those of tetraphenyl porphryin, with a Soret band at 419 nm and four Q bands at 515, 550, 590, and 648 nm. Protonation of the porphyrin with TFA resulted in the expected red shift of the Soret band. Excitation at 419 nm gave an emission at 650 nm. The quantum yield of the porphyrin was determined to be 0.08. Cyclic voltammetry was used to determine the oxidation and reduction potentials of the new porphyrin. Two quasi-reversible one-electron reductions at -1.00 and -1.32 V and a quasi-reversible oxidation at 1.20 V versus the silver/silver chloride reference electrode with tetrabutylammonium tetrafluoroborate as the supporting electrolyte in methylene chloride were observed.     

Silver(Ⅱ) 5,10,15,20-tetra(ethoxycarbonyl) porphyrin:An unexpected six-coordinate linear assembled structure

A novel six-coordinated silver porphyrin linear assembly was observed in silver(II) 5,10,15,20-tetra(ethoxycarbonyl) porphyrin crystal.