酰胺基卟啉的制备,光谱及电化学性质研究

合成了未见文献报道的5-(4-异烟酸酰亚胺基)苯基-10,15,20-三苯基卟啉配体(H2P)及其锌配合物(ZnP),并通过紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等测试方法对化合物的结构加以确认.研究表明,配体和配合物的拉曼光谱有很大区别,卟啉配体的循环伏安曲线与氨基卟啉和锌配合物不同,卟啉环的氧化还原峰位都有移动.差热研究表明,卟啉配体410oC开始分解,显示了很高的热稳定性.     

四(4－N-吡啶基)卟啉衍生物的合成及表征

阳离子卟啉配体;配合物;还原电位;四(4－N-吡啶基)卟啉衍生物的合成及表征     

长链烷基二茂铁取代卟啉的合成与性质

合成了两类长链烷基二茂铁取代的卟啉及其金属锌卟啉,其中一类二茂铁通过酰胺键与卟啉相连,长链在外围(卟啉5与锌卟啉6);另一类二茂铁通过长链与卟啉相连(卟啉7与锌卟啉8).研究了两类卟啉及其金属锌卟啉的光谱与电化学性质.两类卟啉配体的吸收位置几乎相同,与卟啉配体相比,两类金属锌卟啉的最大吸收均收发生了7 nm的红移.荧光光谱中,酰胺键桥连的卟啉5与锌卟啉6的荧光猝灭程度相对增大,量子产率降低.电化学研究表明,当卟啉配体与金属锌离子配位后,卟啉环及二茂铁的氧化还原半波电位均发生负移.此外,将连接二茂铁与卟啉的酰胺键换成长链烷基后,卟啉配体及配合物的第一氧化电势略有降低(13~18 m V),而二茂铁的第一氧化电势却降低182~194m V左右.     

系列羟基苯基卟啉的合成及其荧光光谱研究

按等物质的量比混合两种醛, 采用一步法设计并合成出系列中位取代的对-羟基苯基卟啉, 产物经薄层层析分析表明: 包括六种卟啉配体混合物, 以中性氧化铝为固定相, 采用不同体积比的氯仿和乙醇为淋洗剂, 对六种卟啉配体混合物进行分离, 用波谱方法对六种化合物的结构加以确认. 研究了六种卟啉配体的荧光光谱, 结果显示在440 nm的荧光强度很弱, 随着卟啉周边羟基的增加而增加; 在650 nm的荧光强度很强, 随着卟啉周边羟基的增加而减弱.     

具有圆偏振光特性的卟啉衍生物的合成、表征和CD光谱研究

合成了一组不同碳链的胆甾醇酯侧链卟啉配体和金属Zn配合物. 研究了它们的吸收光谱和发射光谱. 将这些卟啉配体以一定浓度掺杂在聚甲基丙烯酸甲酯(PMMA)中制成固体薄膜, 发现由于在卟啉环上引入了手性的胆甾醇酯侧链, 卟啉化合物在soret带和Q带均有较强的CD吸收, 这种现象可能是卟啉环上的四个手性胆甾醇酯侧链与四苯基卟啉环发生偶合作用. 进一步还发现这些卟啉化合物的圆偏振吸收性质与在PMMA中的浓度有关.     

手性奎宁-卟啉锰催化剂的合成及其催化性能

为了寻找催化活性、相转移活性和手性诱导为一体的卟啉配体[1-4],我们把卟啉和手性相转移源连结起来,用奎宁-卟啉化合物作配体[5],考察其锰 配合物为催化剂对烯烃环氧化反应的催化性能。奎宁-卟啉锰 配合物结构式如下:1　实验部分1.1　试剂和仪器苯乙烯和α-甲基苯乙烯在氮气保护下减压蒸馏处理。氧源ＮａＯＣｌ的浓度由碘量法测定。其余试剂均为化学纯,色谱标样环氧苯乙烯和α-甲基环氧苯乙烯按文献[6]方法合成。奎宁-卟啉配体按文献[5]合成。260-50型红外光谱仪,ＫＢｒ压片;ＵＶ-3000型紫外可见光谱仪,溶剂ＤＭＦ;ＭＴ-3型ＣＨＮ元素…     

具有π共轭骨架的Salen-卟啉型同、异双核配合物的合成及谱学性质

设计合成了两类具有π共轭骨架的Salen-卟啉型配体及金属配合物. 以Salen-卟啉半体及相应的醛为原料, 运用金属模板法合成了单核镍和双核镍Salen-卟啉型金属配合物. 在单核镍的基础上可得到异双核镍、锌Salen-卟啉型金属配合物. 通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱、电喷雾质谱(ESI-MS)和荧光光谱等多种谱学手段对其结构进行了表征. 研究表明, 单核镍及异双核镍、锌配合物中, 镍离子落入Salen 部分的配位空腔, 而锌离子则是与卟啉部分形成锌卟啉大环结构。由于卟啉环流效应及分子π共轭结构的影响, 导致配体上的氢原子的化学位移向高场或低场移动. 当金属离子与配体配位之后,卟啉部分的紫外-可见光谱的Soret带和Q带均发生显著变化, 而荧光则出现猝灭现象.     

5-(4-烟酸酰亚胺基)苯基-10,15,20-三苯基卟啉及其锌配合物的合成及性质研究

合成了未见文献报道的5-(4-烟酸酰亚胺基)苯基-10,15,20-三苯基卟啉配体(H₂P)及其锌配合物(ZnP), 并通过紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等测试方法对化合物的结构加以确认, 研究了配体和配合物的荧光光谱的变化和电化学性质. 热分析研究表明, 卟啉配体及配合物显示了很高的热稳定性, 超过390 ℃才开始分解.     

双-锌卟啉对DABCO分子识别的立体构象及其热力学研究

合成了系列不同长度以柔性侧链相连的p/p型双-锌卟啉配合物,用¹H NMR和UV-Vis研究了不同温度下该系列配合物与刚性双齿配体DABCO(1,4-二氮杂双环)的轴向配位反应,考察了侧链长度对双-锌卟啉与配体的分子识别能力影响。结果表明,主体分子双-锌卟啉可以对客体分子BABCO进行分子识别,合适长度的柔韧烷氧链可以调节主体分子的构象,使DABCO嵌入双卟啉两个卟啉环间空位中,形成锌卟啉-DABCO-锌卟啉三元夹心式配合物构象。探讨了配位反应中立体构象的变化过程,并测定了热力学参数。     

配位负载金属卟啉的合成及催化氧化环已烷的性能研究

合成了三种与咪唑配体键合的新型载体，并通过其与四苯基卟啉铁和卟啉锰配位得到了改性的负载金属卟啉催化剂。讨论了它们在催化氧化环己烷反应中的稳定性、活性等，结果表明配位负载方式明显提高了金属卟啉的稳定性，其中硅胶配位负载锰卟啉还具有较高的活性。     

Application of cyclodextrins in cancer treatment

Four novel porphyrins and their corresponding zinc complexes were synthesized and characterized spectroscopically. Effects of the spacer length of peripheral substituents of porphyrin are investigated in TiO₂-porphyrins hybrid systems by photodegradation of methyl orange in aqueous solution under visible light. The photocatalysts were characterized by means of scanning X-ray diffraction, UV–Vis spectra, X-ray photoelectron spectroscopy and FT-IR spectra. The results indicated that zinc porphyrins were successfully loaded and interacted with the surface of TiO₂ microsphere, which is crucial to enhance the activity of the catalytic composite under visible light. All the new photocatalysts showed much enhanced photoactivity than bare TiO₂. Especially, the photocatalytic activity of 5,10,15-triphenyl-20-[4-(4-naphthoxy)butoxy] phenyl zinc porphyrin-TiO₂ is higher than others.     

Synthesis of phenylethyne-linked porphyrin dyads

Four new porphyrin dyads have been prepared for studies in artificial photosynthesis. The two porphyrins are joined at the meso positions via a phenylethyne linker and are present in zinc/zinc or zinc/free base metalation states. The porphyrin bearing the ethynyl unit incorporates zero, one, or two pentafluorophenyl groups at non-linking meso positions for tuning the porphyrin redox potentials. The synthetic approach entailed Pd-mediated coupling of porphyrin building blocks that bear a single ethynylphenyl or bromo/iodo substituent.     

High-Performance Organic Field-effect Transistors from Functionalized Zinc Meso-Porphyrins

A series of new zinc porphyrins were synthesized, and their charge transport property was tuned by introducing various groups. Triarylamine was introduced to the porphyrin moiety at the meso-position as an electron donor, enhancing the charge carrier mobility. All the synthesized zinc porphyrins are thermally stable with a decomposition temperature over 178 °C. High frontier molecular orbitals levels of these compounds make them stable donor materials. SEM analysis of zinc porphyrins fabricated by spin-coating resulted in diversely self-assembled films. Field-effect transistors were fabricated using bottom-gate/top-contact architecture (BGTC) by solution-processable technique. The higher charge carrier mobility of 5.17 cm²/Vs with on/off of 10⁶ was obtained for trifluoromethyl substituted compound due to better molecular packing. In addition, GIXRD analysis revealed zinc porphyrins films crystalline nature, which supports its better charge carrier mobility. The present investigation has validated that zinc porphyrin building blocks are an attractive candidate for p-channel OFET devices.     

Porphyrins. 19. Intramolecular rearrangement of meso-butyloxymethylporphyrins in sulfuric acid

It was established by the methods of PMR and mass spectrometry that zinc complexes of meso-butyloxymethyletio- and -octaethylporphyrin, when heated in conc. H₂SO₄, are converted to products of the cationic addition of butylene to carbonium ions of the porphyrins. A possible scheme of formation of the new porphyrins and the significance of the reaction discovered for the chemistry of meso-substituted porphyrins are discussed.For Communication 18, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 928–931, July, 1984.     

Synthesis of supramolecular fullerene-porphyrin-Cu(phen)(2)-ferrocene architectures. A heteroleptic approach towards tetrads

Four supramolecular fullerene-porphyrin-Cu(phen)(2)-ferrocene architectures were accessed by a twofold coordination strategy. At first, the phenanthroline-linked zinc porphyrins , conceived as supramolecular synthons, were combined with a ferrocene module, 3,8-(diferrocenylethynyl)phenanthroline, by a Cu(i)-mediated heteroleptic bisphenanthroline complexation (HETPHEN) protocol to furnish the porphyrin-Cu(phen)(2)-ferrocene aggregates . Subsequently, the fullerene module was incorporated by axial pyridyl coordination to the zinc porphyrin, affording . Their suitability as tetrads was interrogated using electrochemical and photophysical data.     

One-pot synthesis of β-carboxy tetra aryl porphyrins: potential applications to dye-sensitized solar cells

A facile one-pot conversion of 2-formyl-5,10,15,20-tetra aryl-substituted porphyrins and their zinc derivatives to the corresponding 2-carboxy-5,10,15,20-tetra aryl-substituted porphyrins was achieved for the first time by using hydroxylamine hydrochloride and phthalic anhydride. All these substituted carboxy porphyrins were completely characterized by using mass, CHN analysis, ¹H NMR, UV-vis, Fluorescence spectroscopies, and cyclic voltammetry. Both the absorption maxima and emission maxima were red shifted by 5-7 nm. The LUMO of these porphyrins are above the TiO₂ conduction band and HOMO was below the redox electrolytes. These carboxy porphyrins are potential applications as sensitizers to dye-sensitized solar cell.     

Preparation, electrochemical and spectral properties of N-methyl-pyridylethynyl nickel porphyrins

A series of nickel N-methyl-pyridylethynylporphines were synthesized and their electrochemical and absorption properties were studied. UV-visible spectra of these complexes show that the absorption red-shifts of the nickel porphyrins are as significant as the zinc analogues. Although the reduction potential shifts caused by the electron-withdrawing substituents are not as large as the zinc complexes, the first reduction potentials of the nickel porphyrins are more positive than those of the zinc counterparts. In addition, the redox behaviors of these nickel porphyrins are similar to those of the zinc analogues.     

Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipolarizabilities, and they may be ascribed as the "mixture" of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic х (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.     

Towards More Photostable,Brighter, and Less Phototoxic Chromophores: Synthesis and Properties of Porphyrins Functionalized with Cyclooctatetraene

Free base and zinc porphyrins functionalized with cyclooctatetraene (COT), a molecule known as a good triplet-state quencher, have been obtained and characterized in detail by structural, spectral, and photophysical techniques. Substitution with COT leads to a dramatic decrease of the intrinsic lifetime of the porphyrin triplet. As a result, photostability in oxygen-free solution increases by two to three orders of magnitude. In non-degassed solutions, improvement of photostability is about tenfold for zinc porphyrins, but the free bases become less photostable. Similar quantum yields of photodegradation in free base and zinc porphyrins containing the COT moiety indicate a common mechanism of photochemical decomposition. The new porphyrins are expected to be much less phototoxic, since the quantum yield of singlet oxygen formation strongly decreases because of the shorter triplet lifetime. The reduction of triplet lifetime should also enhance the brightness and reduce blinking in porphyrin chromophores emitting in single-molecule regime, since the duration of dark OFF states will be shorter.     

One‐Dimensional,Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe₂, R=Br; 2 Zn: E=NMe₂, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]_∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and ¹H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies.