空心酞菁光物理性质的取代基效应

合成了一系列可溶性的2，9，16，23-四取代的空心酞菁，并研究了其光物理性质，实验表明，烷基、烷氧基、芳氧基取代空心酞菁的最低电子跃迁能和最低激发单重态能量与Hammett间位取代基常数线性相关．而强吸电子基如硝基和强给电子基如氨基取代则会诱导分子内电荷转移和使酞菁聚集，导致吸收光谱畸变和激发态量子产率下降．但取代基对酞菁的振动能级没有影响．     

新型可溶性空心酞菁磺酰类化合物的合成及性质研究

以空心酞菁(H2Pc)为原料,采用取代基转化法,经过氯磺酰化和酯化合成了空心酞菁磺酰氯和空心酞菁磺酸对甲氧基苯酯,经元素分析,1H NMR,IR,UV-Vis等方法,确定了空心酞菁磺酰氯和空心酞菁磺酸对甲氧基苯酯的组成分别为H2Pc(SO2Cl)4和H2Pc(SO2-p-OC6H4OCH3)4.结果表明,此两种产物在空心酞菁的苯环上引入取代基后,长波吸收增强,溶解度高,热稳定性良好.     

磺化2,3-萘酞菁锌(Ⅱ)、钴(Ⅱ)的电子吸收光谱和荧光光谱的研究

研究了磺化2，3-萘酞菁锌(Ⅱ)、钴(Ⅱ)在DMF(N，N-二甲基甲酰胺)、DMSO(二甲基亚砜)、乙醇、水等溶剂中的电子吸收光谱和荧光光谱．萘酞菁配合物的Q带与相应的酞菁配合物Q带相比，电子吸收光谱红移80～90nm，荧光光谱红移约100nm，荧光强度也显增加．在金属萘酞菁中引入磺酸基，配合物的电子吸收光谱Q带发生红移，但是影响不大、对于相同中心金属的配合物，改变溶剂的种类对配合物的电子吸收光谱的Q带影响较大．在金属萘酞菁环上引入一个磺酸基时，在相同溶剂中与无取代萘酞菁相比发生荧光光谱Q带红移，荧光强度增大．但在萘酞菁环上继续引入磺酸基时，荧光强度反而减少．磺化萘酞菁钴比磺化萘酞菁锌有较大的荧光强度．不同浓度下的电子吸收光谱和荧光光谱说明金属萘酞菁有集聚倾向、能形成基激缔合物．     

四邻苯二甲酰亚胺基金属酞菁的合成及其性质研究

从氨基酞菁出发，合成它们的衍生物——四邻苯二甲酰亚胺基金属(Cu^Ⅱ和Co^Ⅱ)酞菁，并对相关化合物进行了质谱、紫外可见光谱、红外光谱表征．其紫外可见光谱中Q带有分裂现象．实现了以氨基酞菁为前体物质进行衍生化的合成实验，讨论了取代基的大小、结构、取代位置及酞菁环中心金属的差异对其Q带分裂现象的影响。     

导电酞菁基金属有机框架的高效电催化研究（英文）

在满足日益增长的可持续能源和环境保护需求下,开发用于多种电化学场景的新型催化剂发挥着重要作用。导电酞菁基金属有机框架（MOFs）是一类新型的层叠多孔MOFs,具有面内扩展π共轭结构,可以通过促进传质和电子/电荷转移来增强电催化活性。导电酞菁基MOFs具有优异的导电性,使其在如水、氧、二氧化碳和氮还原等各种电催化反应中非常有前景。导电酞菁基MOFs在电化学能量转换和环境研究中表现出良好的活性。本文主要关注导电酞菁基MOFs,而非其他类型的导电MOFs,并全面概述其导电机理和主要的电催化反应,还将讨论在电催化中使用导电酞菁基MOFs作为非均相催化剂的最新进展。此外,本文将探讨与导电酞菁基MOFs在电催化中的应用的挑战和展望。     

四叔丁基金属酞菁催化活化CO2与环氧丙烷的环加成反应

 以四叔丁基金属酞菁与三正丁胺等有机碱组成的二元催化体系催化活化CO2与环氧丙烷进行环加成反应制备碳酸丙烯酯．同一种金属酞菁与不同有机碱组成的二元催化体系的催化活性与有机碱的碱性强弱一致．有机碱的用量和反应时间对反应均有一定影响，温度对反应的影响较大．与未取代的金属酞菁相比，四叔丁基金属酞菁表现出更高的催化活性．四叔丁基酞菁镁的催化活性高于四叔丁基酞菁铁，在140℃，以四叔丁基金属酞菁镁／三正丁胺为催化剂，碳酸丙烯酯的产率达90．4％．     

酞菁类光电材料研究新进展

酞菁类化合物具有优异的光电响应性能,是光电材料领域最活跃的研究方向之一.评述了酞菁类化合物近几年在不同领域的研究进展,分析总结了酞菁和取代基酞菁的分子结构、晶体形态对光伏材料、薄膜半导体材料、液晶材料、光导材料和电致发光材料等应用性能的影响以及目前存在的问题,最后对酞菁类光电材料的研究和发展前景进行了展望.     

酞菁一富勒烯给受体体系研究进展

酞菁的大π共轭体系使其具有良好的电子给予能力和对可见光的强烈吸收性质,可作为人工光合作用体系中的光捕捉单元．富勒烯具有独特的三维笼状结构,几乎所有反应中都具有低的重组能,是良好的电子或能量受体．将富勒烯与酞菁结合起来,集两个光活性实体于一身,由于酞菁和富勒烯给受体之间的电子相互作用,又赋予其新的性质,具有良好的应用前景,是富勒烯和酞菁领域中的研究热点．本文将酞菁．富勒烯给受体体系分为共价和非共价两种连接方式,介绍其结构与性质以及两者的相互关系,总结了其在有机太阳能电池、非线性光学和液晶性等方面的应用进展,展望了该体系的未来发展趋势．     

可溶性氧钒酞菁的非共振三阶非线性光学性质

合成了不同取代基和不同取代基位置的可溶性氧钒酞菁化合物, 并采用简并四波混频方法测定了这些化合物在非共振条件下的<γ>值和X^(^3^)值, 它们分别在10^-^3^1esu及10^-^1^0~10^-^9esu数量级。酞菁环上取代基的性质将影响化合物的<γ>值, 取代基的给电子能力越强, <γ>值就越大, 而取代基位置对<γ>值的影响较小。     

双吡啶盐/酞菁体系的光诱导电子转移的ESR研究

研究了五种金属酞菁化合物与一系列双吡啶高氨酸盐（PQ2+）之间在苯中的光诱导电子转移．对于酞菁／PQ2+／苯体系，在可见光辐照下，酞菁化合物的价带电子可被激发至导带，然后于界面发生电子转移使PQ2+盐变成离子基PQ+，给出较弱的ESR信号；当有表面活性剂氯代十四烷基吡啶和电子给体三乙醇胺存在时，可使PQ基的ESR信号显著增强5～6信以上．当有氧存在时，PQ+基信号迅速消失，给出较明显的超氧负离子基O2-的信号．氧能严重抑制电子转移的过程．     

New long-chain-substituted polymeric metal-free and metallophthalocyanines by microwave irradiation: Synthesis and characterization

A tetranitrile monomer N,N-bis{2-[2-(3,4-dicyanophenoxy)ethoxy]ethyl}-4-methylbenzenesulfonamide (3) was synthesized by nucleophilic aromatic substitution of N,N-bis[2-(2-hydroxyethoxy)ethyl]-4-methylbenzenesulfonamide (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer 3 in 2-(dimethylamino)ethanol. Ni(II), Co(II) and Cu(II) phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II) and Cu(II) in 2-(dimethylamino)ethanol (DMAE). The Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetate of Zn(II) in DMAE. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis and MS spectral data.     

Synthesis,characterization and electrochemistry of a new organosoluble metal-free and metallophthalocyanines

4-[2-(Phenylthio)ethoxy]phthalonitrile 3 was synthesized by nucleophilic displacement of nitro group in 4-nitrophthalonitrile with 2-(phenylthio)ethanol 1. The metal-free phthalocyanine 4 was prepared by the reaction of a dinitrile monomer with 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I) phthalocyanines 5, 7, 8 were prepared by reaction of the dinitrile compound with the chlorides of Ni(II), Co(II), Cu(I) in DMAE. Zn(II) phthalocyanine 6, was prepared by reaction of the dinitrile compound with the acetates of Zn(II) in DMAE. Electrochemical behaviours of novel metal-free, Co(II) and Zn(II) phthalocyanines were investigated by cyclic voltammetry, potential differential pulse voltammetry techniques. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis and MS spectral data.     

Controlling the nature of mixed (phthalocyaninato)(porphyrinato) rare-earth(III) double-decker complexes: the effects of nonperipheral alkoxy substitution of the phthalocyanine ligand

The half-sandwich rare-earth complexes [M(III)(acac)(TClPP)] (M = Sm, Eu, Y; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate; acac = acetylacetonate), generated in situ from [M(acac)3] x n H2O and H2(TClPP), were treated with 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine [H2{Pc(alpha-OC5H11)4}] (Pc = phthalocyaninate) under reflux in n-octanol to yield both the neutral nonprotonated and protonated (phthalocyaninato)(porphyrinato) rare-earth double-decker complexes, [M(III){Pc(alpha-OC5H11)4}(TClPP)] (1-3) and [M(III)H{Pc(alpha-OC5H11)4}(TClPP)] (4-6), respectively. In contrast, reaction of [Y(III)(acac)(TClPP)] with 1,4,8,11,15,18,22,25-octakis(1-butyloxy)phthalocyanine [H2Pc(alpha-OC4H9)8] gave only the protonated double-decker complex [Y(III)H{Pc(alpha-OC4H9)8}(TClPP)] (7). These observations clearly show the importance of the number and positions of substituents on the phthalocyanine ligand in controlling the nature of the (phthalocyaninato)(porphyrinato) rare-earth double-deckers obtained. In particular, alpha-alkoxylation of the phthalocyanine ligand is found to stabilize the protonated form, a fact supported by molecular-orbital calculations. A combination of mass spectrometry, NMR, UV-visible, near-IR, MCD, and IR spectroscopy, and X-ray diffraction analyses, facilitated the differentiation of the newly prepared neutral nonprotonated and protonated double-decker complexes. The crystal structure of the protonated form has been determined for the first time.     

酞菁氯化铟的固相合成及光敏性能

以尿素、邻苯二甲酸酐、钼酸铵和四水合三氯化铟为原料, 乙酸钠为催化剂, 采用固相法合成酞菁氯化铟, 并用元素分析、UV-Vis、IR和XRD进行了表征. 考察了反应物配比、催化剂、反应温度和时间对产率的影响, 寻找出最佳制备条件为n(尿素)∶n(邻苯二甲酸酐)∶n(三氯化铟)=14∶4.5∶1, 以乙酸钠为催化剂, 130 ℃下恒温0.5 h, 在220 ℃下反应4 h后, 用88％(质量分数)浓硫酸提纯. 研究了酞菁氯化铟光敏电阻薄膜的光敏性能, 结果表明, 当用0.2 g酞菁氯化铟和0.6 g PVB制备光敏电阻薄膜时, 分散介质丁酮-环己酮的最佳用量为36 mL, 其电阻灵敏度保持在1.50×10⁸以上, 积分灵敏度保持在30 μA/(lx·V)以上. 研究结果表明, 酞菁氯化铟光敏电阻薄膜具有很好的光敏性能.     

Lithiumphthalocyanine: Darstellung und Charakterisierung der monoklinen und tetragonalen Modifikationen von LiPc(1-) und der Halogenaddukte LiPc(1-)X (X = Cl,Br, I)

Phthalocyanines of Lithium: Preparation and Characterization of the Monoclinic and Tetragonal Modifications of LiPe(1-) and the Halogene Adducts LiPc (1-)X (X = Cl, Br, I) The preparation of dilithium phthalocyanine (LiPC₂Pc(2-)), tetraalkylammonium lithium phthalocyanines ((TAA)LiPc(2-)), monolithium phthalocyanine hydrate (LiPc(1-)·H₂O), monolithium phthalocyanine (monoclinic and tetragonal modification (m-LiPc(1-), t-LiPc(1-))) and of the halogene adducts with t-LiPc(1-) of the type LiPc(1-)X with X = Cl, Br, I is reported. The UV-VIS, infrared, and resonance raman spectra, the X-ray powder diffractograms, and the measurements of the magnetic susceptibilities and the specific electrical conductivity of the different stable lithium phthalocyanine π-cation radicals are discussed.     

Synthesis and characterization of a new trans-2,2′-azoquinoxaline bridged bisphthalocyanine

A new trans-2,2′-azoquinoxaline bridged bisphthalocyanine was synthesized from the corresponding quinoxaline-2(1H)-one oxime, which can be obtained by the reaction of s-trans-chloroethanedial with 2-(3,4-diaminophenoxy)-9,16,23-tri(hexylthio)phthalocyanine zinc(II). 2-(3,4-Diaminophenoxy)-9,16,23-tri(hexylthio)phthalocyanine zinc(II) was synthesized by reduction of 2-(4-amino-3-nitrophenoxy)-9,16,23-tri(hexylthio)phthalocyanine zinc(II). Novel compounds were characterized by elemental analysis, UV/vis, IR and ¹H NMR spectroscopy. The conductivity and the humidity sensing properties of spin coated films of these compounds were investigated by measuring the complex impedance spectra at different humidities. Films of the final product show up to 10³ orders of magnitude higher conductivity than the starting and intermediate compounds. The results indicate that the presence of water vapour always leads to a drop in the real and imaginary part of the complex impedance. At room temperature, the capacitance of the films exhibits reversible increase with relative humidity, which makes these films attractive for humidity sensing applications.     

Activation of Carbon Dioxide and Synthesis of Propylene Carbonate

Cycloaddition of carbon dioxdie and propylene oxide to propylene carbonate catalyzed by tetra-tert-butyl metal phthalocyanine in the presence of tributylamine(TBA) shows higher yield than catalyzed by unsubstituted metal phthalocyanine.Comparing different catalysts of diverse metals,(t-Bu)4PcMg is more active than (t-Bu)PcFe ,But(t-Bu)4PcCo and (t-Bu)4PcNi only have low catalytic activities towards the reaction.Moreover,the yield will increase as the temperature increases.     

A new polymeric phthalocyanine containing 16-membered tetrathia macrocyclic moieties by microwave irradiation: Synthesis and characterization

Tetranitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer with 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile in 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I)-phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II) and Cu(I) in DMAE. Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetates of Zn(II) in DMAE. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.     

Lanthanide complexes of alkylsulfamoyl-substituted phthalocyanines

The extra-ligand complexes obtained in the reaction of tetra-4-[6′,8′-di(N,N-diethylsulfamoyl)-2′-naphtyloxy]phthalocyanine with erbium or ytterbium acetylacetonates were characterized by elemental analysis, IR and electronic spectroscopy.     

Synthesis and study of properties of the sulfonaphthylazophenoxyphthalonitrile and related phthalocyanine

The 4-[4′-(5-sulfonaphthylazo)phenoxy]phthalonitrile potassium salt was synthesized by the reaction of 4-chlorophthalonitrile with 5-(4′-hydroxyphenylazo)-1-naphthalenesulfonic acid, and on its basis was obtained tetra-4-[4′-(5-sulfonaphthylazo)phenoxy]phthalocyanine. The products were characterized by elemental analysis, IR and electron spectroscopy. The effect of the introduced substituent on the spectral and other properties of the synthesized compounds was demonstrated.