Synthesis and properties of cobaltacarborane-functionalized Zn(II)-phthalocyanines

The syntheses of two new A₃B-type Zn(II)-phthalocyanines (Zn-Pcs) containing either one or two cobaltacarborane residues are reported, and the X-ray structure of a key phthalonitrile precursor is presented. The Zn-Pcs are highly soluble and exist as monomers in polar organic solvents.     

卟啉和酞菁修饰的单壁碳纳米管的合成及光谱性质

利用5-(4-氨基苯基)-10,15,20-三(3,5-二辛氧基苯基)卟啉和2,9,16-三叔丁基-23-氨基锌(Ⅱ)酞菁通过酰胺键连接方式同时对单壁碳纳米管进行共价修饰, 通过红外光谱、拉曼光谱、X射线光电子能谱和透射电镜对所得碳纳米管复合物进行了表征, 证实了其结构. 紫外-可见吸收光谱和荧光光谱分析表明, 光活性分子卟啉和酞菁均与单壁碳纳米管之间存在较强的电子效应. 经卟啉和酞菁共同修饰的单壁碳纳米管复合物比卟啉和酞菁单独修饰的碳纳米管复合物的吸光范围更宽, 而且分散性较好(309 mg/L), 是潜在的光电转换材料.     

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     

酞菁金属配合物的合成及光谱特性研究

以4-叔丁基邻苯二甲酸酐、金属（Co3+、Al3+、Zn2+）氯化物、尿素、钼酸铵为原料,用固相合成法分别合成系列酞菁类金属配合物（MPc）。通过目标产物的红外谱图和紫外图,确定形成MPc;对合成的MPc的紫外可见吸收、荧光光谱特性进行研究,考察溶剂、浓度、中心金属对MPc化合物的光谱特性的影响,为光谱理论理解和实验教学提供桥梁。     

以偶氮苯基团为周边取代基的锌酞菁的合成及光物理性质

合成了两种带有偶氮苯周边取代基的锌酞菁化合物,并对其进行了结构表征.与一般酞菁的吸收光谱相比,偶氮苯酞菁的UV-Vis光谱的B带吸收峰强度明显强于Q带.该类化合物在光照条件下表现出重复性较好的顺反异构化性质.Z-扫描结果表明,这类化合物的三阶非线性光学性能主要来源于酞菁的非线性折射率,且β位取代的酞菁的三阶非线性效应大于α位取代的,顺反异构对酞菁的三阶非线性光学性能的影响不大.     

四取代羧基酞菁锌与白蛋白共价结合物的制备与光谱性质

通过成酰胺键的方式制备了一系列含羧基酞菁和白蛋白(牛血清白蛋白(BSA),人血清白蛋白(HSA))之间的共价结合物,所涉及到的酞菁分别是α-四(4-羧基苯氧基)酞菁锌(1)和α-四[4-(2-羧基乙基)苯氧基]酞菁锌(3),以及它们相应的β位四取代酞菁锌(化合物2和4).比较了游离酞菁以及它们的白蛋白结合物在磷酸盐缓冲溶液(PBS)中的光谱性质.结果表明,当酞菁被共价固定于白蛋白大分子上之后,展现出比游离酞菁更明显的单体特征吸收,而且结合物中的酞菁光谱特征不受体系pH值变化的影响.羧基在酞菁环上的取代位置,对酞菁与白蛋白结合前后的光谱转变幅度有影响,α位取代比β位取代更有利于光谱的变化.化合物1和3的白蛋白共价结合物在PBS溶液中甚至呈现出单体形式为主的光谱特征,Q带最大吸收波长分别位于697和706nm附近.     

A novel metal-free and metallophthalocyanines containing four 19-membered dithiadiazadioxa macrocycles by microwave irradiation: Synthesis and characterization

The novel tetrasubstituted metal-free phthalocyanine (5) and metallophtalocyanines (6, 7 and 8) bearing four 19-membered dithiadiazadioxa macrocyclic moieties on peripheral positions have been synthesized by cyclotetramerization reaction of phthalonitrile derivative (4) in a multi-step reaction sequence. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.     

Microwave-assisted synthesis and characterization of a new metal-free and metallophthalocyanines

Dinitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 4-phenoxyphenol (1) with 4-nitrophthalonitrile (2). The metal-free phthalocyanine (4) was prepared by the reaction of dinitrile monomer (3) with DMAE. Ni(II), Co(II), and Zn(II) metallophthalocyanines were prepared by the reaction of 3 with chlorides of Ni(II), Co(II), and Zn(II) in DMAE. The new compounds were characterized by IR, ¹H- and ¹³C-NMR, UV-Vis, elemental analysis, and MS specral data.     

Synthesis of non-peripherally substituted tetra(dihexylmalonate) alcohol soluble phthalocyanines

Dimethyl-(2,3-dicyanophenyl)malonate was prepared by the reaction of dimethylmalonate and 3-nitrophthalonitrile. A cyclotetramerization reaction of dimethyl-(2,3-dicyanophenyl)malonate with the corresponding divalent metal salt was achieved in hexanol in the presence of DBU, affording the non-peripherally substituted tetra(dihexylmalonate) Cu(II), Pd(II), and Co(II) phthalocyanines. Transesterification occurred under these reaction conditions, so that methyls in the phthalonitrile derivative were converted into hexyl groups during phthalocyanine formation in hexanol. The new compounds were characterized by elemental analyses, FT-IR, ¹H-NMR, ¹³C-NMR, UV-Vis, and mass spectral data.     

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．     

Synthesis and Spectroscopic Properties of a Series of New tetra-Substituted Metal Phthalocyanines

A new class of metal phthalocyanines（MPcs） containing four 8-quinolinol（8-QH） derivative moieties were successfully synthesized and characterized by mass spectroscopy, IR, UV-Vis and element analysis, the results of which were consistent with the proposed structures. All of them can dissolve in common organic solvents, such as dichloromethane, chloroform, and acetone. The effect of metal ion on the absorption of Q band was studied with UV-Vis spectra. The fluorescent properties for those complexes were also investigated.     

Synthesis,characterization, conduction,and dielectric properties of tetra tert-butylsulfanyl substituted phthalocyanines

The tert-butylsulfanylphthalonitrile has been prepared with optimized synthetic procedure. Metal free (H₂Pc) and metallo phthalocyanines (Pcs) (ZnPc, CoPc, CuPc, PbPc) have been synthesized by cyclotetramerization of tert-butylsulfanylphthalonitrile in the presence of DBU and metal salts. Thus, tert-butylsulfanyl groups enhance the solubility, shift the Q band absorption to the red visible region, and inhibit efficient cofacial interaction of the Pcs (2–6) as evaluated by UV–vis spectra. The electrical conduction and dielectric properties of the synthesized Pc thin films sandwiched between indium tin oxide and aluminum electrodes (ITO–Pc–Al) were investigated from 300 to 500 K. At low bias voltage the conduction is ohmic while at high bias voltage the conduction becomes space charge limited with an exponential distribution of traps. The measured ac conductivity data are discussed in terms of classical models based on pair approximation. It was found that the ac conductivity obeys the power law given by σ_ac = σ₀ω^s, in which the frequency exponent s decreases with temperature. The real and imaginary parts of the impedance are found to be dependent on both frequency and temperature.     

Synthesis and Spectroscopic Properties of Acridinium-9-sulfonamides

By introducing an electro-withdrawing antipyrine group, N-(p-toluenesulfonyl)-N-(4-antipyrine)-10-methylacridinium-9-carboxamide triflate is prepared. The UV, fluorescent (FL), and chemiluminescent (CL) properties of the target compound and of its precursor are investigated by comparing with those of the model compounds N-(p-toluenesulfonyl)-N-phenyl-10-methylacridinium-9-carboxamide triflate and the corresponding precursor, respectively. The results show that, compared with the corresponding model compound, acridine sulfonamide with a heterocyclic antipyrine group exhibits blue shift of both UV absorption and of maximum excitation wavelength (λ_ex) and the emission wavelength (λ_em) in FL spectra. The λ_ex of the final target and its precursor are 268 and 274 nm, respectively, and the λ_em are 321 and 327 nm, respectively, whereas the λ_ex of the model compound and its unmethylated precursor are 365 and 359 nm, respectively, and the λ_em are 504 and 440 nm, respectively. Moreover, the chemiluminescence of the final target compound triggered by H₂O₂ could finish within 1.1 s, and the quantum yield is similar to that of the model compound, being 5.6 times high as that of luminol.     

Low-Symmetry Phthalocyanines Bearing Carboxy-Groups: Synthesis,Spectroscopic and Quantum-Chemical Characterization

The synthesis and characterization of A₃B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.     

Cobaltacarborane-phthalocyanine conjugates: Syntheses and photophysical properties

Syntheses of two new cobaltacarborane-phthalocyanine conjugates, one anionic (Pc 6) and one zwitterionic (Pc 7), were accomplished via cyclotetramerization of the corresponding cobaltacarborane-substituted phthalonitriles (4 or 5) with excess phthalonitrile in quinoline. X-ray structures of two phthalonitrile precursors (2 and 3) were obtained and are discussed, and the absorption and emission properties of the two cobaltacarborane-phthalocyanine conjugates in several solvents were investigated. The anionic conjugate 6 exists mainly as a monomer in polar organic solvents and has fluorescence quantum yields in the region 0.2-0.3. The zwitterionic conjugate 7 aggregates in solution and displays lower quantum yields ∼0.1 in organic solvents.     

Synthesis, photophysical and electrochemical properties of perfluoroisopropyl substituted binuclear phthalocyanine conjugated with a butadiyne linker

Synthesis of 1,3-butadiyne-bridged perfluoroisopropyl binuclear phthalocyanine 2 has been successfully achieved from unsymmetrical A₃B-type iodo-perfluoroisopropyl phthalocyanine by palladium-catalyzed cross-coupling with trimethylsilylacetylene and copper-catalyzed Glaser homo-coupling as key reactions. The dyad 2 essentially remains non-aggregated irrespective of solvent and concentration. Electrochemical analysis suggests oxidation is not possible whereas the molecule is more easily reduced. All the results are advantages for photodynamic therapy (PDT).     

Design and Synthesis of Novel Pegylated 4‐Methylcoumarins

Coumarins are well known for their antioxidant and anti‐edema activities. Their antioxidant property gets enhanced with a methyl group at the C‐4 position of the pyran ring. To increase the antioxidant potential and their hydrophilicity, a lipase (Novozyme 435) catalyzed copolymerization of 4‐methylcoumarin diesters and polyethylene glycols (PEGs) has been carried out to give novel copolymers.     

Synthesis and Spectroscopic Properties of S-,O-Substituted Naphthoquinone Dyes

New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were synthesized via vinilic substitution. 2,3-Dichloro-1,4-naphthoquinone gave 3a and 4b with 4,4′-thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction of 2,3-dichloro-1,4-naphthoquinone with cyclohexylmercaptane. The compounds 9d and 10 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-1,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro analysis, FT-IR, ¹H NMR, ¹³C NMR, MS, UV-Vis, and fluorescence spectroscopy.     

Synthesis,electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric characterization of new metal-free and metallophthalocyanines substituted with 4-{2-[2-(1-naphthyloxy)ethoxy]ethoxy} groups

The synthesis of novel metal-free and metallophthalocyanines [Ni(II), Zn(II), Co(II), Cu(II)] were prepared by cyclotetramerization of a novel 4-{2-[2-(1-naphthyloxy)ethoxy]ethoxy}phthalonitrile and the corresponding metal salts (NiCl₂, Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The structures of the target compounds were confirmed using elemental analysis, IR, ¹H NMR, ¹³C NMR, UV–Vis and MS spectral data. Voltammetric and in situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, metal-free, and zinc phthalocyanines show only ring-based reduction and oxidation processes. All complexes decomposed and coated on the electrode as nonconductive film at positive potential window of the electrolyte. An in situ electrocolorimetric method has been applied to investigate color of the electro-generated anionic and cationic forms of the complexes.     

Synthesis of new axially-disubstituted silicon-phthalocyanine derivatives: optical and structural characterisation

This paper describes the synthesis of a range of new axially-disubstituted silicon-phthalocyanines with several ester and ether derivatives as axial ligands, including phenyl, terphenyl, thienyl and pyrenyl systems. Their absorption and emission spectra are reported and fluorescence lifetimes and quantum yields are correlated with the ligand structures. The X-ray crystal structure of a new polymorph of silicon-phthalocyanine bis(3-thienyl)acetate 7 is described.