酞菁分子结构特征对复合凝胶玻璃体系光限幅性能的影响

用溶胶凝胶法将2组具有不同分子结构特征的酞菁配合物分别植入二氧化硅凝胶基质,制备均匀掺杂的复合凝胶玻璃,并对其光限幅性能进行测试。研究结果表明:掺杂酞菁分子结构特征对其复合体系的光限幅性能有显著影响。掺杂无金属酞菁(phthalocyanine, H2Pc)和不同金属酞菁配合物(metallophthalocyanine, MPc)的硅氧凝胶玻璃,其光限幅效应随中心离子不同而异,并依 H相似文献   

四-α（β）-（4-吡啶氧基）酞菁锌的光物理性质研究

测定了新合成的α位取代和β位取代的四-(4-吡啶氧基)酞菁锌配合物的UV-Vis吸收光谱、荧光光谱及激发单重态寿命、纳秒瞬态吸收光谱与激发三重态寿命.在此基础上,与相关配合物进行了比较,探讨了取代基及其取代位置对酞菁锌配合物的吸收光谱、激发单重态寿命及激发三重态寿命的影响.     

四-P-（2-醛基苯氧基）取代酞菁锌的合成及其吸收光谱的研究

以4-（2-醛基苯氧基）二甲腈和无水氯化锌为原料,固相法合成了周环取代的酞菁锌。产物经MS、IR和UV/Vis表征。在与相同中心金属的四苯氧基取代酞菁锌相比较的基础上,探讨了其UV/Vis光谱中的Q带位置与溶剂极性的关系。     

四-β-(2-醛基苯氧基)取代酞菁锌的合成及其吸收光谱的研究

以4-(2-醛基苯氧基)邻苯二甲腈和无水氯化锌为原料,固相法合成了周环取代的酞菁锌.产物经MS、IR和UV/Vis表征.在与相同中心金属的四苯氧基取代酞菁锌相比较的基础上,探讨了其UV/Vis光谱中的Q带位置与溶剂极性的关系.     

不对称席夫碱Cu(Ⅱ)配合物的合成和催化性能研究

用2,4-二羟基苯乙酮、二胺基硫脲与取代水杨醛反应,合成了3种不对称席夫碱配体及其Cu(Ⅱ)配合物,通过元素分析、1HNMR、IR、UV-vis、MS等手段对配体及其配合物进行了组成和结构表征,并研究了不对称席夫化合物对双氧水的催化分解性能。结果表明,合成得到的不对称席夫碱Cu(Ⅱ)配合物对催化H2O2分解具有较好的催化性能。     

酞菁铕镨钕配合物的合成及表征

本文研究了铕酞菁、钕酞菁利镨酞菁配合物的合成、提纯与表征的方法。合成及表征结果表明,合成所得酞菁化合物通过元素分析可知具有纯度高;红外光谱表征推测结构可靠。紫外分析表明铕酞菁、钕酞菁和镨酞菁配合物特征吸收峰有相似之处。     

酞菁铕镨钕配合物的合成及表征

研究了铕酞菁、钕酞菁和镨酞菁配合物的合成、提纯与表征的方法。合成及表征结果表明，合成所得酞菁化合物通过元素分析可知，具有纯度高、红外光谱表征推测结构可靠。紫外分析表明铕酞菁、钕酞菁和镨酞菁配合物特征吸收峰有相似之处。     

金属酞菁及其取代衍生物的结构与光电性能研究进展

由于取代方式的不同,使得金属酞菁衍生物数目庞大,结构各异。晶体结构的不同,造成配合物光电性能等多种性质的改变。酞菁类光敏材料研究方法有溶剂调节法,相转移法、溶胶-凝胶法、气相沉积法和真空热蒸发等,这些技术调变了酞菁衍生物的光电导性能,在光动力疗法等领域意义重大。酞菁类气敏材料对某些气体具有选择性高、响应灵敏等特点,可用于气体传感器的制作。建议进一步探讨取代金属酞菁衍生物的光敏、气敏机理,以便在分子层次上优化设计分子的结构,改善材料性能,拓宽应用范围。     

金属酞菁敏化剂的合成及性质研究

以4-羧基邻苯二甲酸酐、尿素和金属盐为主要原料,采用固相合成法合成了四羧基取代的系列金属酞菁;4-羧基邻苯二甲酸酐、邻苯二甲酸酐、尿素、氯化锌为主要原料,合成单羧基酞菁锌.用红外光谱和紫外-可见光谱对其主要基团进行了表征,并比较了这些金属酞菁的紫外-可见光潜,以及用循环伏安法研究了金属酞菁配合物的电化学性质.     

酞菁配合物在光限幅中的应用

酞菁配合物是一种很有前途的光限幅材料,具有特殊的结构和优良的光限幅性能,已引起人们极大的兴趣。综述了近年来酞菁配合物光限幅材料的研究,并展望了今后的研究方向。     

The synthesis of asymmetrically substituted amphiphilic phthalocyanines and their gas-sensing properties

A series of asymmetrically substituted amphiphilic phthalocyanines have been synthesized. They have been deposited as Langmuir–Blodgett films onto glass and/or glass substrates bearing aluminum interdigitated electrode patterns. The films show fast response to NO₂ with almost complete recovery at room temperature. It is indicated that layer ordering and molecular packing within the LB films are important factors determined the gas-sensing properties.     

Comparative electrocatalytic behavior of self-assembled monolayer of thiol derivatised Co (II) phthalocyanines on gold disk, ultramicro cylinder and fiber electrodes

This paper reports on the use of thiol derivatised cobalt phthalocyanines as self assembled monolayers (SAMs) on gold disk electrode, gold ultramicro-cylinder electrode (UMCE) and on gold coated fiber for the detection of l-cysteine. The complexes are peripherally and non-peripherally substituted with phenylthio substituents. The SAM modified electrodes showed enhancement of catalytic currents and overpotential reduction occurred on the gold modified electrodes with different geometries. Electrocatalytic oxidation of l-cysteine on SAM modified gold coated fiber was reported for the first time. The gold coated fiber and ultramicro cylinder electrode were less stable towards the electrocatalytic oxidation of cysteine compared to its oxidation on the gold disk. The gold disk electrode gave better catalytic performance in terms of stability and reduction of overpotential.     

Synthesis and characterization of solubility enhanced metal-free phthalocyanines for liquid crystal display black matrix of low dielectric constant

For the liquid crystal display (LCD) black matrix (BM) with a low dielectric constant and high light absorption property, it is advantageous to employ dyes instead of carbon black or pigments. For this purpose, the dyes should have high solubility in industrial organic solvents. For improved solubility in industrial solvents, three metal-free phthalocyanines (PC), peripherally substituted with bulky groups, were synthesized and dye-based BMs were fabricated. The solubility as well as the spectral and thermal properties of the dyes were examined, and the optical, thermal and dielectric properties of a dye-based black matrix were tested. The greenish phthalocyanine dyes with high molar extinction coefficients and high thermal stability showed enhanced solubility in industrial solvents as a result of the greater steric hindrance among the dye molecules and higher affinity between the dye molecules and solvents. The dye-based BMs had low dielectric constants and exhibited superior optical properties and satisfactory thermal stability.     

Synthesis and properties of phthalocyanine zinc(II) complexes replaced with oxygen and sulfur linked adamantane moieties

Novel, zinc (II) phthalocyanines substituted with 2-adamantanol and 1-adamantanethiol moieties were prepared from the corresponding phthalonitriles employing commercially available 3- and 4-nitrophthalonitrile as the starting material. The Q-band of tetra-α-substituted phthalocyanines occurred at longer wavelengths than those of the corresponding, tetra-β-substituted phthalocyanines. Substituents at the β position increased Φ_F values; all phthalocyanines studied displayed excellent singlet oxygen generations ability, with α-substituted dyes showing higher Φ_Δ values than their β-isomers. The dyes exhibited good photo-stability, with α-substituted phthalocyanines proving to be of higher stability than the corresponding β-isomers.     

Water-soluble quaternized mercaptopyridine-substituted zinc-phthalocyanines: Synthesis, photophysical, photochemical and bovine serum albumin binding properties

The synthesis and characterization of the new zinc phthalocyanine derivatives, tetra- (non-peripheral, 5) and octa-(peripheral, 6) substituted with 2-mercaptopyridine and their respective quaternized derivatives (8 and 9) are reported. Photochemical and photophysical properties of the new complexes are compared with those of the previously reported peripherally tetra-substituted complexes 7 and 10. The quaternized compounds exhibit excellent solubility in water, making them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. Spectroscopic, aggregation, photophysical and photochemical properties of these complexes are also investigated and compared. Photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yield) properties of these phthalocyanine photosensitizers are very important for the assessment of these complexes as PDT agents. In this study, the effects of the position of the substituents and quaternization of the substituents on the photophysical and photochemical parameters of the zinc phthalocyanines are also reported. This study also showed that the water-soluble quaternized zinc phthalocyanines strongly bind to blood plasma proteins such as bovine serum albumin (BSA).     

Microwave-assisted synthesis and characterization of the monomeric phthalocyanines containing naphthalene-amide group moieties and the polymeric phthalocyanines containing oxa-aza bridge

New naphthalene-amide substituted phthalocyanines and oxa-aza bridge polymeric phthalocyanines were prepared by conventional and microwave methods. The chlorides of Cu(I), Ni(II) and Co(II) were employed in order to synthesize the corresponding metal phthalocyanines and Zn(CH₃COO)₂ was used for the preparation of the zinc phthalocyanines. For the preparation of the Co-containing phthalocyanines, ammonium molybdate had to be added as catalyst. In the microwave-assisted synthesis, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DMAE (dimethylaminoethanol) was used as a solvent. The solubility of the phthalocyanines containing naphthalene-amide group (1a–e, 3a–e) is low in ethanol, ethyl acetate, chloroform, DMF and DMSO. Polymeric phthalocyanines (2a–e) are not soluble in common organic solvents such as chloroform, DMF and DMSO but are soluble in dilute H₂SO₄.     

Synthesis and properties of phthalocyanine zinc(II) complexes replaced with oxygen and sulfur linked adamantane moieties

Novel, zinc (II) phthalocyanines substituted with 2-adamantanol and 1-adamantanethiol moieties were prepared from the corresponding phthalonitriles employing commercially available 3- and 4-nitrophthalonitrile as the starting material. The Q-band of tetra-α-substituted phthalocyanines occurred at longer wavelengths than those of the corresponding, tetra-β-substituted phthalocyanines. Substituents at the β position increased Φ_F values; all phthalocyanines studied displayed excellent singlet oxygen generations ability, with α-substituted dyes showing higher Φ_Δ values than their β-isomers. The dyes exhibited good photo-stability, with α-substituted phthalocyanines proving to be of higher stability than the corresponding β-isomers.     

Theoretical aspects of the structure of polymeric phthalocyanines

Recent work on theoretical aspects of the structure of planar and stacked polymeric phthalocyanines is discussed. The regular structure of planar bridged polymeric phthalocyanines can be described mathematically by assuming the whole molecule placed in a Cartesian coordinate system. The resulting structure model agrees with analytical data. For example, the equationn=64/v ², wheren is the number of phthalocyanine macrocycles in a planar bridged polymeric phthalocyanine andv (derived from IR spectra) is the number of end group-carrying bis(phthalonitrile) units per phthalocyanine ring, is derived from this model. An extended structure model yields fractal dimensions for planar bridged polymeric phthalocyanines. The positions of the bridges or substituents in bridged planar polymeric phthalocyanines cause different symmetries and different numbers of positional isomers for which equations are derived. Linear bridged and rectangular planar polymeric phthalocyanines have approximatelyi _d/4 isomers, while square bridged planar polymeric phthalocyanines possess abouti _d/8 isomers. Stacked substituted polymeric phthalocyanines have approximatelyi _d/16 isomers, wherei _d is the number of isomers which can be drawn on paper (i _d=2 ^m ;m is the number of substituted phathalonitrile monomers in the polymeric phthalocyanine). The possible symmetries for polymeric planar and stacked phthalocyanines are discussed. Previous discussions of symmetry and numerical notation of stacked polymeric phthalocyanines with tetrasubstituted phthalocyanine rings are extended in this work.Presented in part as a poster at the IUPAC 5th International Conference on Macromolecule-Metal Complexes, Bremen, Germany, 1993.     

Oxidation of cyclohexane over copper phthalocyanines encapsulated in zeolites

The oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid has been studied using phthalocyanines and substituted (chloro- and nitro-) phthalocyanines of copper, cobalt and iron encapsulated in zeolites X and Y, at ambient conditions and using molecular oxygen as well as alkyl (tertiary butyl, cyclohexyl and cumyl) hydroperoxides as the oxidants. The catalytic efficiencies of the encapsulated materials are much higher than those of the neat complexes. The rate of oxidation of cyclohexane using copper hexadecachloro phthalocyanine- encapsulated Y zeolite catalysts is quite high (TOF=400 h^-1) with TBHP efficiencies which can reach upto 90%. The isolated encapsulated metal complex is the active site. Solvents exert a major influence on product distribution (cyclohexanol, cyclohexanone and adipic acid are the major products). Byproducts like succinic and glutaric acids are not formed when using acetonitrile as the solvent. Rates of oxidation when using the alkyl hydroperoxides as oxidants decrease with an increase in their molecular cross-section (cyclohexyl>t-butyl>cumyl) confirming that the active site is indeed located inside the zeolitic cavities and not on the external surface. This revised version was published online in July 2006 with corrections to the Cover Date.     

RNA nucleoside recognition by phthalocyanine-based molecularly imprinted polymers

Highly selective molecularly imprinted polymers (MIPs) having a phthalocyanine-based recognition centre as receptors for RNA nucleoside were prepared. In particular, a zinc phthalocyanine peripherally substituted with methacrylic groups was synthesized and utilized as functional monomer in combination with methacrylic acid (MAA) to form polymers with the aim to obtain MIPs having improved binding capacity and selectivity for nucleosides. Tri-O-acetyladenosine (TOAA) was utilized as model template in the preparation of the MIPs. The corresponding non metallated phthalocyanine was also prepared and used as functional monomer for the preparation of the MIPs in order to understand the role of the Zinc(II) ion in the binding capacity of the polymers towards the template molecule. The MIP prepared by using both the zinc phthalocyanine and MAA showed higher binding ability towards TOAA compared to the MIPs prepared using only MAA or its combination with the non metallated phthalocyanine. The results obtained suggest that the nucleoside is specifically bound to the polymer through multi-point interactions involving both the coordination of the nucleoside to the metal of the phthalocyanine and hydrogen bonding/electrostatic interactions with MAA and the modifiers linked to the phthalocyanines. As for the selectivity, the MIPs exhibited relative high binding affinities for TOAA while they did not show any binding capacity for the other RNA nucleosides.