Phthalocyanine polymers. II. Synthesis and characterization of some metal phthalocyanine sheet oligomers

Metal phthalocyanine oligomers that possess peripheral carboxylic acid groups were prepared by the reaction of pyromellitic dianhydride, a metal salt, urea, and a catalyst. These materials have blue to purple colors with a metallic luster and are soluble in sulfuric acid, dimethylsulfoxide, dimethylformamide, and dimethylacetamide. Their thermal stability is high in an anaerobic atmosphere with char yields of 80–85% at 800°C. Elemental, spectral, and titrimetric analyses and thermal studies were carried out to characterize them.     

Phthalocyanine

Phthalocyanines, which have been produced for 75 years as blue and then as green pigments, are the most important organic colorants. Their mostly planar aromatic π‐system provides color‐fastness, ‐homogeneity, ‐intensity and ‐stability, combined with a simple synthetic access, which are prerequisites for its use as a colorant. In recent years, phthalocyanins have also found applications in CD/Rs, as blue and green colors in LCDs, as photoconductors in laser printers, and as p‐conductors and absorbers in organic solar cells. The system exhibits a great structural variability (different substituents at and metals/semimetals in the ligand) in order to tune different properties. Because of these presuppositions the phthalocyanines have a great potential for new applications also in other fields.     

酞菁和酞菁铜的电子结构与光谱

用ＩＮＤＯ／ＣＩ方法研究了酞菁和酞菁铜的电子结构和紫外－可见光谱。对酞菁采用共享氢模型。酞菁铜的一个单电子位于１１ｂ１ｇ（ｄｘ＾２－ｙ＾２）的ＭＯ上。从酞菁铜与酞菁，分子对称性由Ｄ４ｈ降低为Ｄ２ｈ，谱线发生分裂。计算结果基本与实验结果相符。     

Phthalocyanine polymers. III. Poly(nickel phthalocyanine)benzimidazole as a novel high-temperature-resistant polymer

A new type of poly(nickel phthalocyanine)benzimidazole was prepared by the condensation reaction between nickel (11) 4,4′,4″,4″′-phthalocyanine tetracarboxylic acid dihydrate and 3, 3′-diaminobenzidine. The reaction was investigated by both the melt and solution condensation methods. This polymer showed good thermal and thermo-oxidative stability. Also noteworthy is its high thermal stability with a char yield of 88% at 800°C in nitrogen. No catastrophic decomposition was observed up to 1100°C. A qualitative study of decomposition in both air and nitrogen is presented. Elemental analyses agreed well with the proposed structure. Infrared (IR) and thermogravimetric analysis (TGA) studies were performed to characterize this polymer, and isothermal gravimetric analysis was done to determine its long-term thermal stability. The apparent activation energies for the thermal degradation in air and nitrogen are given.     

酞菁键合硅胶的制备及分离取代酞菁异构体

制备和表征了一种新的酞菁键合硅胶，三-β-(辛巯基)-β-(磺酰胺基)-酞菁铜键合硅胶。研究了该键合酞菁硅胶作为HPLC固定相的基本色谱性能。实验结果表明，该固定相可以分离四-α-(2，2，4-三甲基-3-戊氧基)酞菁(铜、镍)的4种异构体，也可以观察到四-α-(2，2，4-三甲基-3-戊氧基)无金属酞菁的4种异构体，而商业C₁₈(VERTEX Eurospher)却只能观察到两组峰，表明这种酞菁键合硅胶固定相在分析、分离一些取代酞菁异构体方面比商业C₁₈具有更好的分离效果。     

Phthalocyanine polymers. V. Novel type of thermally stable polyimides derived from metal phthalocyanine tetraamines and pyromellitic dianhydride

New poly(metal phthalocyanine) pyromellitimides of copper, cobalt, nickel, and zinc were synthesized and elemental, IR, TGA, and inherent viscosity measurement studies were done to characterize these polymers. They showed exceptional thermal and thermo-oxidative stability with char yields at 800°C ranging from 75 to 87% in a nitrogen atmosphere. The ratio of the polymer decomposition temperatures in air and nitrogen (PDT) (air)/PDT (N₂) varied from 0.91 to 0.97, which indicated that the onset of degradation of these polymers is greatly affected by the presence of an oxidizing atmosphere. Isothermal studies were done to evaluate the long-term thermal stability of these polymers.     

纳米酞菁氧钛(TiOPc)的制备及光敏性能

纳米酞菁氧钛(TiOPc)的制备及光敏性能;有机光导材料     

Conductivity of One-Dimensional Phthalocyanine Compounds

Phthalocyanine, compounds(MPcL) containing the bridge radical ligand were studied by using the method of EHMOACC. Calculation results indicate that the charge carriers are mainly from thermal excitation of semiconductor, where charges are transferred by both hole and electron; the information manifested in the electron energy band and electric conductivity deduced by means of migration formula of the charge carrier at room temperature are in accordance with the experiment facts in the main.     

Phthalocyanine polymers. IV. Novel type of thermally stable polyimides derived from metal phthalocyanine tetramines and benzophenone tetracarboxylic dianhydride

Poly(metal phthalocyanine)imides of copper, cobalt, nickel, and zinc were synthesized by the reaction of metal phthalocyanino tetramines with benzophenone tetracarboxylic dianhydride. These polymers were characterized by elemental analyses and IR, TGA, and inherent viscosity studies. Noteworthy features of these phthalocyanine polymers are their remarkable thermal and thermooxidative stabilities with char yields at 800°C that range from 78 to 83% in a nitrogen atmosphere. The relative thermal stabilities of these polymers have been evaluated by activation energy measurements.     

Carboxy-substituted Phthalocyanine Metal Complexes

Metal complexes of carboxy-substituted phthalocyanines differing in the number of carboxy groups and their positions and those having carboxy groups together with other substituents were synthesized, and their spectral and some other properties were studied.     

真空沉积酞菁铅和酞菁氧钒层状纳米复合膜的吸收光谱研究

有机光电材料在 2 0世纪 80年代后期得到了快速发展 ,与无机材料相比 ,它不仅价格低廉 ,易于加工 ,选择范围广 ,而且还可以通过分子结构的裁剪实现性能优化 [1～ 3 ] ,目前已成为光电导领域研究中的一个热点 .采用不同种类的化合物进行分子间复合能使材料的光电导性能得到一定程度的改善 [4 ,5] ,如提高光谱响应范围及调节禁带宽度 (用于激光器件的制造 )等 .本研究小组在真空蒸发沉积金属酞菁复合膜方面做了一些工作 ,发现真空共蒸发沉积的复合膜的吸收光谱相对于单一金属酞菁膜的吸收光谱有明显的加宽和红移现象 [6] .本文尝试用层状复合…     

Phthalocyanine and polystyrene film nanocomposites

The organic solvent was shown to determine the structure of copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc) in the CuPc-polystyrene composite during the formation of the latter. The structure and morphology of the resulting nanocomposite films was studied by atomic force and transmission electron microscopy. Different physical structures of CuPc formed in different solvents (cyclohexane, toluene, chloroform, and trichloroethylene).     

聚苯乙烯对酞菁铜颜料微胶囊化的研究

自１９５４年美国首先将微胶囊化应用于无碳复写纸后［１,２］,这项技术在药物、农药、食品及染料等方面已得到广泛应用［３］．微胶囊（ＭＣ）直径通常是１～５０００μｍ,构造分为囊壁和囊芯两部分［４］．囊壁材料大多使用高分子材料,少数用无机物［５］．有机颜料...     

Gold(II) Phthalocyanine Revisited: Synthesis and Spectroscopic Properties of Gold(III) Phthalocyanine and an Unprecedented Ring‐Contracted Phthalocyanine Analogue

In 1965, gold(II) phthalocyanine (AuPc, 1 ) was described to be synthesized from unsubstituted 1,3‐diiminoisoindoline and gold powder or AuBr. Compound 1 has been regarded as a rare example of a paramagnetic gold(II) complex. However, its chemistry, especially the oxidation state of the central gold ion, has not been previously explored due to the inherent insolubility of 1 caused by its unsubstituted structure. In our attempt to synthesize soluble AuPcs by using 5,6‐di‐substituted 1,3‐diiminoisoindolines, gold(III) phthalocyanine chloride ( 3 ) and a gold(III) complex of an unprecedented ring‐contracted phthalocyanine analogue ([18]tribenzo‐pentaaza‐triphyrin(4,1,1), 4 ) were isolated. With this discrepant result from the original literature in hand, a reinvestigation of the original AuPc synthesis by using unsubstituted 1,3‐diiminoisoindoline and various gold salts (including gold powder and AuBr) was performed, finding that only unsubstituted analogues of 3 and 4 or free‐base phthalocyanine were obtained. No gold(II)‐containing species could be isolated.     

含酞菁功能基聚苯乙烯的光电导性能研究

合成了新型含酞菁功能基聚苯乙烯，该聚合物具有优良的溶解性能和成膜能力，同时又有一定的光电导性，对该聚合物的染料增感研究发现结晶紫，孔雀绿对于该聚合物均有增感作用，较大幅度地提高了光电导性．采用ＥＳＲ和荧光光谱的研究表明，该聚合物的光电导机理可能是形成了电荷转移络合物．     

酞菁铜溶解性研究及其电沉积薄膜的制备

通过测定α-酞菁铜(α-CuPc)在4种不同的有机溶剂中的紫外可见光吸收光谱,研究了不同溶剂以及加入不同量的三氟乙酸(TFAA)对酞菁铜溶解性和质子化的影响.以溶解性研究为基础,探讨了在电化学沉积法制备酞菁铜薄膜时不同工艺条件对其形貌的影响.实验结果表明:加入TFAA后,酞菁铜在硝基甲烷和氯仿中溶解良好,而且在氯仿中更容易质子化;使用扫描电镜(SEM)表征,结果表明TFAA及酞菁铜摩尔含量对薄膜制备的影响最为明显.     

溶剂热法直接合成酞菁铜晶体

以喹啉为溶剂, 在反应釜中将1,3-二异吲哚、钼酸铵和二水乙酸铜在喹啉中反应, 降至室温后得到长10.5 mm针状的酞菁铜单晶, 最佳的反应条件: 以10 mL喹啉为溶剂, 于270 ℃反应8 h, 产率为51.3%.