Synthesis and photophysical properties of annulated dinuclear and trinuclear phthalocyanines

Metal-free mononuclear, dinuclear and trinuclear phthalocyanines were prepared by a mixed cyclotetramerisation of a 1,2,4,5-tetracyanobenzene derivative and 4,5-bis(2,6-dimethylphenoxy)phthalonitrile. For the first time, a pi-electron-conjugated trinuclear phthalocyanine was synthesised with phthalocyanine units connected by common annulated benzene rings. The Q band of the trinuclear compound in solution occurs at lambda = 944 nm whereas those of the dinuclear and mononuclear compounds are at lambda = 853/830 and 701/664 nm, respectively. Fluorescence quantum yields, fluorescence lifetimes and singlet-oxygen quantum yields of the compounds were determined.     

Design of novel substituted phthalocyanines; synthesis and fluorescence,DFT, photovoltaic properties

The 4-(2-[3,4-dimethoxyphenoxy] phenoxy) phthalonitrile was synthesized as the starting material of new syntheses. Zinc, copper, and cobalt phthalocyanines were achieved by reaction of starting compound with Zn(CH3COO)2, CuCl2, and CoCl2 metal salts. Basic spectroscopic methods such as nuclear magnetic resonance electronic absorption, mass and infrared spectrometry were used in the structural characterization of the compounds. Absorption, excitation, and emission measurements of the fluorescence zinc phthalocyanine compound were also investigated in THF. Then, structural, energy, and electronic properties for synthesized metallophthalocyanines were determined by quantum chemical calculations, including the DFT method. The bandgap of HOMO and LUMO was determined to be chemically active. Global reactivity (I, A, η, s, μ, χ, ω) and nonlinear properties were studied. In addition, molecular electrostatic potential (MEP) maps were drawn to identify potential reactive regions of metallophthalocyanine (M-Pc) compounds. Photovoltaic performances of phthalocyanine compounds for dye sensitive solar cells were investigated. The solar conversion efficiency of DSSC based on copper, zinc, and cobalt phthalocyanine compounds was 1.69%, 1.35%, and 1.54%, respectively. The compounds have good solubility and show nonlinear optical properties. Zinc phthalocyanine gave fluorescence emission.     

THE EFFECTS OF PHOTODYNAMIC THERAPY USING DIFFERENTLY SUBSTITUTED ZINC PHTHALOCYANINES ON VESSEL CONSTRICTION, VESSEL LEAKAGE AND TUMOR RESPONSE

Abstract— The effects of four different zinc phthalocyanines were studied during and after photodynamic therapy (PDT). Measurements of vessel constriction, vessel leakage, tumor interstitial pressure, eicosanoid release, and tumor response of chondrosarcoma were made in Sprague-Dawley rats. Animals were injected intravenously with 1 μmol/ kg of mono-, di-, or tetrasulfonated zinc phthalocyanine, or 1 μmol/kg of a zinc phthalocyanine substituted with four tertiary butyl groups. Tissues were exposed to 400 J/cm² 670 nm light 24 h after photosensitizer injection. An additional group of animals was given indomethacin before treatment. The use of the monosulfonated and tertiary butyl substituted zinc phthalocyanines in PDT caused the release of specific eicosanoids, caused vessel constriction, and induced venule leakage and increases in tumor interstitial pressure. Tumor cures of 27% and 7% were observed. Photodynamic therapy using the disulfonated zinc phthalocyanine did not induce vessel constriction or the release ofeicosanoids, however; tumor cure was 43%. The use of thc tetrasulfonated zinc phthalocyanine caused intermediate effects between the mono- and disulfonated compounds. The administration of indornethacin to animals completely inhibited the effects of PDT using the monosulfonated compound but had minimal effects on treatment using the disulfonated compound. This suggests that the monosulfonated and disulfonated compounds act by different mechanisms of destruction.     

双核钴锰酞菁对SOCl2还原反应的电催化性能

为了确定双核金属酞菁化合物对亚硫酰氯还原反应是否具有比单核金属酞菁更强的电催化性能, 通过循环伏安测试方法, 用酞菁钴和酞菁铁作为对比, 研究了双核钴锰酞菁在1.5 mol·L-1 LiAlCl4/SOCl2电解液中的电催化行为, 并计算出动力学参数, 由此来评估具有平面结构的双核金属酞菁化合物对亚硫酰氯还原的催化活性的影响. 通过比较循环伏安曲线发现, 与单核酞菁钴(II)和酞菁铁(II)相比, 双核钴锰酞菁对SOCl2还原反应具有更好的催化活性, 能提高SOCl2还原反应的交换速率常数和SOCl2在玻碳电极上的扩散系数, 从而提高SOCl2还原电位和电流.通过ER14250型实体电池10 mA放电性能测试验证表明, 与单核酞菁钴和酞菁铁催化剂的电池相比, 双核钴锰酞菁在低温(-30 ℃)下可提高放电中点电压0.3 V, 在常温(25 ℃)下可以提高放电容量约100 mAh, 催化效果比单核酞菁钴和酞菁铁显著.     

具有Cn对称性的大分子的能带结构研究 1: 计算方法

利用环间和环内Bloch函数建立了一组新的原子轨道基函数。首次设计了适用于一维具有旋转对称性的大环分子的能带程序。计算了酞菁、四氮卟吩、四苯并卟啉, 四苯基卟啉的能带结构, 较好地解释了卟啉类化合物导电性能不如酞菁类的事实。还计算了酞菁铜和酞菁锰的能带结构, 讨论了酞菁与酞菁简化模型的能带结构以及晶体轨道的差异。     

Cellulose bearing covalently linked copper phthalocyanine trisulphonate as an adsorbent selective for polycyclic compounds and its use in studies of environmental mutagens and carcinogens.

A method useful as a preconcentration technique for isolating mutagens and carcinogens is described. Cotton bearing covalently linked copper phthalocyanine trisulphonate as ligand (blue cotton) can adsorb selectively compounds having three or more fused rings. The adsorption takes place in aqueous media, involving 1:1 complex formation between the ligand and the polycyclic compound. The desorption can be done by elution with organic solvents, most effectively with methanol containing ammonia. As many important environmental mutagens and carcinogens are polycyclics, this adsorption is useful as a means of extracting this class of materials from crude samples such as food, urine and river waters. The use of copper phthalocyanine as a ligand for chromatographic supports has recently been initiated, yielding promising results for the effective separation of polycyclic aromatic compounds from each other.     

Phthalocyaninodehydroannulenes

4-Bromo- and 4,5-dibromo-3,6-dibutoxyphthalonitrile have been prepared and treated with 3,6-didecylphthalonitrile in cross tetramerisation reactions in the presence of nickel acetate to afford monobromo- and dibromo-dibutoxyhexadecylphthalocyaninato nickel(II) complexes. Sonogashira and Stille coupling reactions on these compounds displaced the bromine substituents by ethynyl groups. Oxidative coupling of the monoethynyl derivatised nickel phthalocyanine afforded a butadiynyl-linked dinuclear phthalocyanine. The corresponding coupling reaction of the diethynylated phthalocyanine gave a mixture of phthalocyaninodehydroannulenes. Separation of the mixture yielded the diphthalocyaninodehydro[12]annulene as the major product. Electrospray mass spectrometry provides evidence for its aggregation in solution. The corresponding cyclic trimer, the triphthalocyaninodehydro[18]annulene, has been identified as a minor product. Both compounds show a large splitting of the Q-band absorption in the visible region spectrum. Most of the mononuclear phthalocyanine precursors exhibit discotic liquid crystal behaviour. The diphthalocyaninodehydro[12]annulene also enters a mobile phase on heating, but undergoes an irreversible change at 220 degrees C. MALDI-TOF mass spectrometry of the product reveals that the compound undergoes oligomerisation at this temperature.     

The Synthesis of New Phthalocyanines Substituted with 12-Membered Diazadioxa Macrocycles

 A macrocyclic diazadioxa dibromo compound was synthesized by ring closure of 1,2-bis-(2-iodoethoxy)-4,5-dibromo-benzene and 1,4-bis-(p-tolylsulfonyl)-ethylenediamine. Its phthalonitrile derivative was obtained by cyano substitution. This diazadioxa macrocyclic dibromo derivative was directly converted into the copper(II) phthalocyanine by reaction with CuCN in tetramethyl urea. Conversion of this phthalonitrile derivative into the metal-free phthalocyanine was accomplished by refluxing with DBU. The zinc(II) phthalocyanine was prepared by reaction of the dinitrile derivative with Zn(OAc)₂ in quinoline. The lutetium bis-(phthalocyaninate) complex was obtained by treating the dinitrile derivative with anhydrous lutetium acetate and DBU in 1-hexanol. The new compounds were characterized by elemental analyses and IR, ¹H NMR, mass, UV/Vis, and ESR spectra.     

Controlling the directionality of charge transfer in phthalocyaninato zinc sensitizer for a dye-sensitized solar cell: density functional theory studies

Density functional theory (DFT) calculation on the molecular structures, charge distribution, molecular orbitals, electronic absorption spectra of a series of eight unsymmetrical phthalocyaninato zinc complexes with one peripheral (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent at 2 or 3 position as an electron-withdrawing group and a different number of electron-donating amino groups at the remaining peripheral positions (9, 10, 16, 17, 23, 24) of the phthalocyanine ring, namely ZnPc-β-A, ZnPc-β-A-I-NH(2), ZnPc-β-A-II-NH(2), ZnPc-β-A-III-NH(2), ZnPc-β-A-I,II-NH(2), ZnPc-β-A-I,III-NH(2), ZnPc-β-A-II,III-NH(2), and ZnPc-β-A-I,II,III-NH(2), reveals the effects of amino groups on the charge transfer properties of these phthalocyanine derivatives with a typical D-π-A electronic structure. The introduction of amino groups was revealed altering of the atomic charge distribution, lifting the frontier molecular orbital level, red-shift of the near-IR bands in the electronic absorption spectra, and finally resulting in enhanced charge transfer directionality for the phthalocyanine compounds. Along with the increase of the peripheral amino groups at the phthalocyanine ring from 0, 2, 4, to 6, the dihedral angle between the phthalocyanine ring and the average plane of the (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent increases from 0 to 3.3° in an irregular manner. This is in good contrast to the regular and significant change in the charge distribution, destabilization of frontier orbital energies, and red shift of near-IR bands of phthalocyanine compounds along the same order. In addition, comparative studies indicate the smaller effect of incorporating two amino groups onto the 16 and 17 than on 9 and 10 or 23 and 24 peripheral positions of the phthalocyanine ring onto the aforementioned electronic properties, suggesting the least effect on tuning the charge transfer property of the phthalocyanine compound via introducing two electron-donating amino groups onto the 16 and 17 peripheral positions. As expected, compound ZnPc-β-A-I,III-NH(2) with four amino groups at 9, 10, 23, and 24 positions of the phthalocyanine ring shows the best charge transfer directionality among the three phthalocyaninato zinc complexes with four peripheral amino groups.     

Weak epitaxy growth and phase behavior of planar phthalocyanines on p-sexiphenyl monolayer film

We systematically investigated the weak epitaxy growth (WEG) behavior of a series of planar phthalocyanine compounds (MPc), i.e., metal-free phthalocyanine (H2Pc), nickel phthalocyanine (NiPc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), grown on a p-sexiphenyl ( p-6P) monolayer film by selected area electron diffraction (SAED) and atomic force microscopy (AFM). Two types of epitaxial relations, named as incommensurate epitaxy and commensurate epitaxy, were identified between phthalocyanine compounds and the substrate of the p-6P film. The tiny variation of the lattice constant of phthalocyanine compounds can result in different crystal orientations. The change rule of incommensurate and commensurate epitaxy was extracted. The tendency of commensurate epitaxy becomes weaker as the lattice constant b increases, while it gets stronger as the substrate temperature is elevated. Large size and continuous H2Pc films can be obtained by controlling the growth conditions. The WEG method is generally applicable in the whole family of planar phthalocyanine compounds and may be used to fabricate other high-quality organic films.     

The nature of chromaticity of triphenylmethane,xanthene, phthalocyanine,and thiazine dyes

Works concerned with the origin of coloration of organic compounds are reviewed. Proofs are given that individual triphenylmethane, xanthene, phthalocyanine, and thiazine dye molecules do not absorb light in the visible range and are not chromogens, that is, do not determine compound chromaticity. Individual molecules of these dyes should be considered chromophoric particles, necessary but insufficient for coloration generation. Elementary chromogens of the dyes under consideration are dimers (supramolecular particles). The blue coloration of aromatic compound azulene has a similar origin.     

2,3,9,10,16,17,24,25-Octakis(octyloxycarbonyl)phthalocyanines. Synthesis, spectroscopic, and electrochemical characteristics

A series of three novel 2,3,9,10,16,17,24,25-octakis(octyloxycarbonyl)phthalocyanine compounds M[Pc(COOC8H17)8] (M = 2H, Cu, Zn) (1-3) have been synthesized via the cyclic tetramerization of 4,5-di(octyloxycarbonyl)phthalonitrile, which was obtained by a newly developed procedure with o-xylene as starting material, promoted with organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in the absence and presence of metal salt like M(acac)2.H2O (M = Cu, Zn) in n-octanol at 120 degrees C. In addition to elemental analysis, these novel octakis(octyloxycarbonyl)-substituted phthalocyanine compounds have been characterized by a series of spectroscopic methods. The electrochemistry of these compounds was also studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. A significant shift to the positive direction for both the first oxidation and the first reduction of compound 1, relative to H2Pc, reveals the electron-withdrawing nature of octyloxycarbonyl groups attached to the peripheral positions of phthalocyanine. The effect of peripheral octyloxycarbonyl substitution on the electrochemistry of the series of phthalocyanines 1-3 has been reasonably explained by theoretical calculation results using the density functional theory (DFT) method.     

The Synthesis of New Phthalocyanines Substituted with 12-Membered Diazadioxa Macrocycles

Summary.  A macrocyclic diazadioxa dibromo compound was synthesized by ring closure of 1,2-bis-(2-iodoethoxy)-4,5-dibromo-benzene and 1,4-bis-(p-tolylsulfonyl)-ethylenediamine. Its phthalonitrile derivative was obtained by cyano substitution. This diazadioxa macrocyclic dibromo derivative was directly converted into the copper(II) phthalocyanine by reaction with CuCN in tetramethyl urea. Conversion of this phthalonitrile derivative into the metal-free phthalocyanine was accomplished by refluxing with DBU. The zinc(II) phthalocyanine was prepared by reaction of the dinitrile derivative with Zn(OAc)₂ in quinoline. The lutetium bis-(phthalocyaninate) complex was obtained by treating the dinitrile derivative with anhydrous lutetium acetate and DBU in 1-hexanol. The new compounds were characterized by elemental analyses and IR, ¹H NMR, mass, UV/Vis, and ESR spectra. Received May 8, 2001. Accepted (revised) June 25, 2001     

Highly photostable silicon(IV) phthalocyanines containing adamantane moieties: synthesis, structure, and properties

Two new axially disubstituted silicon(IV) phthalocyanines 1 and 2 have been synthesized by treating silicon phthalocyanine dichloride with 1-adamantanemethanol or 1-adamamtaneethanol, respectively. The crystal structure of compound 2 has been characterized by X-ray diffraction analysis. Both compounds are efficient singlet-oxygen generator with a quantum yield of 0.40-0.43. With two rigid bulky adamantane moieties at the axial positions, these phthalocyanines not only are essentially non-aggregated in common solvents, but also exhibit a high photostability. They are about 100 times more stable than zinc phthalocyanine under the same irradiation conditions. With the goal of enhancing the biocompatibilities, interactions and conjugations of these two compounds with bovine serum albumin have also been investigated.     

稀土单酞菁化合物的NMR研究

研究了从Sm^3^+到Lu^3^+(Gd^3^+除外)九个稀土单酞菁化合物的^1H NMR化学位移.发现对重稀土化合物,酞菁环上α、β质子诱导位移符号的变化呈现"三个一组效应".即,"Tb^3^+、Dy^3^+、Ho^3^+化合物,^1H共振谱线移向高场,而对Er^3^+、Tm^+^3、Yb^3^+化合物,则移向低场.化学位移的最大变化发生在4f^8构型(Tb^3^+)处.所得结果与Bleaney理论一致.测得部分稀土单酞菁化合物的^1^3C NMR谱,讨论了化学位移的变化.     

负载空间链四(6-氨基己酸磺酰基)铝氯酞菁聚合物纳米粒子的合成及其离体光动力活性

以四磺酸铝氯酞菁1为原料,采用氨基转化法,经磺酰氯化和Hinsberg磺酰胺化反应合成四磺酰铝氯酞菁2和四(6-氨基己酸磺酰基)铝氯酞菁3,产物结构经元素分析,IR,1HNMR和MS-ESI表征。3在磷酸盐缓冲溶液中与两亲嵌段共聚物聚乙二醇-聚-L-赖氨酸(PEG-b-PLL)通过静电自组装,形成负载3的聚合物纳米粒子3/m。原子力显微镜(AFM)和透射电子显微镜(TEM)表明3/m具有球形核壳结构,直径约为10～20 nm。紫外-可见吸收光谱和荧光光谱法研究了3/m的光物理性质。通过对不同孵育时间的人脐带血内皮细胞(HUVEC)摄取药代动力学测定3/m细胞摄取率和MTT法评价3/m的离体光动力活性,相对自由酞菁3,3/m的细胞摄取率大大提高,且提前1 h达到最高浓度,而且细胞抑制率明显增大,约为3的2倍。     

Microwave-assisted synthesis and characterization of phthalocyanines substituted with azo compound containing eugenol moiety

The new metallophthalocyanines (Co, Ni, Cu, and Zn) substituted with azo compound containing eugenol moiety are described. Firstly, azo compound (I) containing eugenol moiety was synthesized by treating eugenol with p-hydroxyaniline. Then phthalonitrile compound (1) was synthesized by microwave-assisted synthesis method. The purification of phthalonitrile compound (1) was carried out by column chromatographic separation. Intramolecular hydrogen bonding in the azo compound (I) prevent base-catalyzed nucleophilic aromatic substitution of OH group belongs eugenol. At the last step, metallophthalocyanines (1a, 1b, 1c, and 1d) were synthesized by the microwave irradiation. The microwave-assisted synthesis method reduces reaction times and enhances the yield of the reactions. All phthalocyanine compounds are soluble in DMF and DMSO. The structures were confirmed by elemental analysis, ¹H NMR, ¹³C NMR, UV/Vis, IR and Mass spectra.     

TWO NEW STERICALLY HINDERED PHTHALOCYANINES: SYNTHETIC AND PHOTODYNAMIC ASPECTS

The synthesis and the properties of 1,4-dibutoxy-2,3-dicyanotriptycene, of a metal-free tetradibenzobarrelenooctabutoxyphthalocyanine, and of the corresponding zinc phthalocyanine are described. The two phthalocyanines do not aggregate when dissolved in benzene at concentrations up to 450 microM. For the metal-free and the zinc compounds, the red band maxima are at 736 and 757 nm, the triplet maxima are at 590 and 605 nm, the triplet state lifetimes are 58 and 177 microseconds, and the protoporphyrin-IX dimethyl ester-to-compound bimolecular rate constants for triplet energy transfer are 2.61 x 10(8) and 1.47 x 10(8) M-1 s-1. Triplet energy transfer from the metal-free compound to O2 is endoergonic by 1.0 kcal mol-1. The potential of the zinc compound for photodynamic therapy is touched upon.     

New type of tetrazine‐substituted metallophthalocyanines by microwave irradiation: Synthesis and characterization

5,6‐bis(4‐methylphenyl)‐2,3‐dihydro‐1,2,3,4‐tetrazine 2 was synthesized by the dimerization of ethyl p‐methylbenzoateformylhydrazone 1 in hydrazinehydrate solution. 2,3‐bis(4‐methylphenyl)‐6,7,14,15‐tetrahydro[1,2,3,4]tetrazino [2,3d][1,8, 4,5]benzodithia‐diazecine‐10,11‐dicarbonitrile 4 was sythesized by cyclization reaction of tetrazine monomer 2 onto 1,2‐bis‐(2‐iodoethylmercapto)‐4,5‐dicyanobenzene 3 . Co(II) and Cu(II) phthalocyanine complexes were prepared by reaction of the dinitrile compound ( 4 ) with the chlorides of Co(II), Cu(II), and DMAE at 175°C, 350 W in a microwave oven for 10 min. Zn(II)‐phthalocyanine complex was prepared by reaction of the dinitrile compound 4 with the acetate of Zn(II) and DMAE at 175°C, 350 W in a microwave oven for 10 min. The new compounds were characterized by a combination of IR, ¹H‐NMR, ¹³C NMR, UV‐vis, elemental analysis, and MS spectral data. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:456–461, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20623     

Selective metal sensor phthalocyanines bearing non-peripheral functionalities: Synthesis,spectroscopy, electrochemistry and spectroelectrochemistry

A novel alcohol-soluble ionophore ligand and its non-peripherally tetrasubstituted functional 1,8,15,22-tetrakis(6-hydroxyhexylsulfanyl) metallophthalocyanines M[Pc(α-SC₆H₁₂OH)₄] (M = Cu(II), Zn(II), Co(II); Pc = phthalocyanine) are reported. The aggregation and cation binding behaviors of the phthalocyanine compounds in the presence of soft Ag^I and Pd^II metal ions were investigated by using UV–Vis spectroscopy. The new compounds have been characterized by elemental analysis, IR, ¹H, ¹³C NMR, UV/Vis spectroscopy, ESI and MALDI–TOF–MS mass spectra. Voltammetric and in-situ spectroelectrochemical studies show that while copper and zinc phthalocyanine complexes give well-defined ring-based reduction and oxidation processes, the cobalt phthalocyanine gives both metal-based and ring-based redox processes which have reversible and diffusion controlled character.