Synthesis and Properties of Tetra- and Octasubstituted Metal Pthalocyanines with Alkylsulfamoyl Groups

Sulfochlorination of sulfophenyl- and halosulfo-substituted copper and cobalt phthalocyanines and the subsequent reaction of the resulting sulfonyl chlorides with various alkylamines afforded a series of tetra- and octasubstituted metal phthalocyanines containing alkylsulfamoyl groups. Their solubilities, spectral, and other physicochemical properties are dependent on the number and length of the alkyl radicals, the nature of the substituent combined with the alkylsulfamoyl group, and the nature of the complexing metal.     

5,10,15,20-四(4-羧基苯基)卟啉的微波合成

利用微波加热法,由5,10,15,20-四(4-甲氧羰基苯基)卟啉水解合成了四(4-羧基苯基)卟啉,并对反应条件进行了探讨。结果表明：以吡啶为溶剂,氢氧化钾为催化剂,以65W的微波功率辐射30rnin,可使5,10,15,20-四(4．甲氧羰基苯基)卟啉完全水解。反应时间是传统加热法用时的1/48。     

新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁配合物的合成及其光物理性质

高锰酸钾降解2-萘酚-6-磺酸钠合成了"分子碎片"4-磺酸钾基邻苯二甲酸(1)。1在钼酸铵催化下,用固相法合成了四-磺酸铝酞菁(2)。采用氨基转化的方法,2经磺酰氯化和Hinsberg磺酰胺化反应分别合成了四-磺酰氯铝酞菁(3)和新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁(4)。1～4结构经1HNMR,IR,MS和元素分析表征,并对4的光物理性质进行了初步研究。     

Copper Tetra-4-Carboxyphthalocyanine as a Chemical Additive and Dye for Composites and Polycaproamide

Copper tetra-4-carboxyphthalocyanine was studied as a chemical additive and dye for a polymeric binder of fibrous composites and polycaproamide.     

Synthesis of Tetra- and Triarylantimony Fluorobenzoates

Pentaarylantimonies Ar₅Sb (Ar = Ph, p-Tol) was reacted with triarylantimony bis(perfluorobenzoate) and bis(3,4,5-trifluorobenzoate) in toluene at elevated temperature to obtain tetraarylantimony fluorobenzoates in 90% yield. Triarylantimony bis(fluorobenzoates) were prepared in an yield of up to 98% from triarylstibine and fluorobenzoic acid by oxidative addition in ether in the presence of hydrogen peroxide.     

Synthesis and Properties of Tetra-4-{[(1,1'-biphenyl)-4-yl]oxy}phthalocyanines and Their Sulfonic Acid Derivatives

The template condensation of 4-{[(1,1'-biphenyl)-4-yl]oxy}phthalonitrile with cobalt, copper, and magnesium acetate resulted in the synthesis of metal phthalocyanines. Sulfochlorination of the latter followed by hydrolysis gave the corresponding sulfonic acid derivatives. The spectral characteristics and chemical properties of the synthesized compounds were studied.     

四叔丁基四氮杂卟啉配合物的合成、热稳定性及光限幅特性研究

采用无金属四氮杂卟啉与金属盐回流的方法合成了2种四叔丁基四氮杂卟啉配合物，其中四叔丁基四氮杂卟啉铅(II)配合物未见文献报道。研究了该2种配合物及其配体的电子吸收光谱行为、热稳定性及在532 nm对8 ns激光的光限幅特性。结果表明：该类配合物的Q带的最大吸收峰值λ_max在570~630 nm之间，B带的最大吸收峰值λ_max在330~350 nm之间，随中心金属离子不同，Q带吸收峰位置有明显差异；配合物在氮气气氛中的起始分解温度大于250 ℃，其在热重图上的失重过程对应着4个取代基(-C(CH₃)₃)的脱去，共轭大环在500 ℃以下没有分解；它们的光限幅机制属于激发三重态的反饱和吸收(RSA)，其中四氮杂卟啉铅配合物具有更强的光限幅效应，这与铅的重原子效应有关。     

氧化铜纳米晶的合成及性能研究

通过水热方法,合成出CuO纳米片,类纳米花等纳米结构,X光衍射表明样品为单斜CuO,透射电镜和高分辨透射电镜表征了样品的形貌和尺寸,观察到CuO纳米晶是由小的晶粒聚集而成的多晶结构。同时讨论了实验中各实验参数在合成CuO纳米晶时所起的作用： KOH具有促进CuO结晶的作用;十六烷基三甲基溴化铵可以控制反应产物尺寸;柠檬酸钠能够影响纳米粒子的排布规则程度,从而进一步影响CuO纳米晶的形貌和尺寸。另外我们还研究了CuO纳米片的光学性能和氮气吸附性质。     

Synthesis and Structure of Tetra- and Triarylantimony Oximates

Pentaphenyl- and penta-p-tolylantimony were reacted with benzophenone oxime or triarylantimony bis(benzophenonoximate) in toluene to obtain tetraarylantimony benzophenonoximate. Triarylantimony bis(benzophenonoximates) were prepared by oxidative addition from tryarylstibine and oxime in ether in the presence of hydrogen peroxide. X-ray diffraction analysis of tetraphenylantimony benzophenonoximate was performed to show that coordination of the antimony atom is trigonal-bipyramidal and the oxime oxygen atom is axial.     

Synthesis and Structures of Tetra- and Triarylantimony Oximates

Tetraphenylantimony acetophenoneoximate (I) and tetra-n-tolylantimony 3-nitrobenzaloximate (II) were synthesized by reacting pentaarylantimony with oxime or triarylantimony dioximate in toluene. Tri-n-tolylantimony bis(acetophenoneoximate) (III) and triphenylantimony bis(cyclohexanoneoximate) (IV) were synthesized by reacting triarylantimony with oxime and hydrogen peroxide. The structures of compounds I–IV were determined using X-ray diffraction analysis. The antimony atoms in I–IV are coordinated to the axial oxime groups to form a distorted trigonal bipyramid. The Sb–C(Ph) and Sb–O bond lengths and Sb...N intramolecular contacts in structures I and II lie within 2.114–2.135, 2.137–2.154, and 2.857–2.871 Å, respectively; the respective values in structures III and IV are 2.097–2.112, 2.058–2.080, and 2.779–2.874 Å.     

Synthesis and Structure of Tetra- and Triphenylantimony Organosulfonates

Tetraphenylantimony 2-naphthalenesulfonate (I), tetraphenylantimony phenylmethanesulfonate (II), and bis(tetraphenylantimony) sulfate (III) were synthesized via reaction of pentaphenylantimony with 2-naphthalenesulfonic acid, triphenylantimony bis(phenylmethanesulfonate), and triphenylantimony sulfate, respectively, in toluene. Triphenylantimony bis(phenylmethanesulfonate) (IV) was synthesized from triphenylstibine, phenylmethanesulfonic acid, and hydrogen peroxide (taken in the molar ratio of 1 : 2 : 1). Organoantimony betaine (V) was obtained by reacting triphenylstibine with phenylmethanesulfonyl chloride in the presence of hydrogen peroxide. The structures of the compounds synthesized were determined using X-ray diffraction analysis. The Sb atoms in I–IV have distorted trigonal bipyramidal coordination. The Sb–C and Sb–O distances are equal to 2.100(4)–2.140(3) and 2.644(2) Å in molecule I, 2.105(2)–2.131(2) and 2.699(1) Å in II, 2.096(6)–2.169(6) and 2.101(6), 2.271(3) Å in III, and 2.101(3)–2.102(5) and 2.111(2) Å in IV. In V, the Sb atoms have close tetrahedral (2.105–2.115 Å) and remote (2.65, 3.019 Å) octahedral environment (the oxygen atoms of sulfo group of their own and neighboring molecules). Two betaine molecules are joined through the O atoms of the sulfo groups of bidentate phenylmethanesulfonate ligands to form a centrosymmetrical dimer. The intermolecular C(1)–H(1)···O(1) hydrogen bonds (3.10 Å) are formed that strengthen the dimer.     

Synthesis and Structure of Tetra- and Triarylantimony Oximates

Reactions of pentaphenyl- and penta-p-tolylantimony with benzophenone oxime or triarylantimony bis(benzophenone oximate) yield tetraarylantimony benzophenone oximates. Triarylantimony bis(benzophenone oximates) were prepared by oxidative addition from triarylstibine and benzophenone oxime in the presence of hydrogen peroxide. X-ray diffraction analysis was performed to show that benzophenone oxime is a dimer and tetraphenylantimony benzophenone oximate has a trigonal bipyramidal antimony atom and an axial oxime oxygen atom.     

四-β -(8-喹啉氧基)取代酞菁金属配合物的合成、表征及其荧光性质研究

本文利用DBU催化法合成得到4种四-β-(8-喹啉氧基)取代酞菁金属配合物(金属分别为钴、镍、铜、锌)，同时分别进行了元素分析、UV-Vis、IR光谱、质谱表征。还对四-β-(8-喹啉氧基)取代酞菁金属配合物进行了荧光性质研究，为其进一步应用提供依据。     

Association of Copper Tetra-4-(n-alkoxycarbonyl)phthalocyanines in Solvents with Low Dielectric Permittivity

Association of copper tetra-4-(n-butoxycarbonyl)- and copper tetra-4-(n-nonoxycarbonyl)phthalocyanines in benzene and chloroform was studied. It was found that the length of the alkyl chain has no noticeable effect on the association; the solvent effect is somewhat stronger. The thermodynamic parameters of dimerization were calculated.     

Atypical Film-Forming Behavior of Soluble Tetra-3-Nitro-Substituted Copper Phthalocyanine

Thin films of metal phthalocyanines (MPc) are known to exhibit excellent physical properties but poorly controlled morphologies. Therefore, the present work seeks to understand the film growth mechanism of a model compound for potentially usable MPc, specifically, copper tetra(3-nitro-5-tert-butyl)phthalocyanine (CuPc*). The Langmuir-Schaefer (LS) technique was applied to prepare a series of CuPc* films under different processing conditions. The film growth was examined by Brewster angle microscopy (BAM) on the water surface and small-angle X-ray scattering (SAXS) from the solid films. Neutron reflectometry (NR) measurements of the water uptake into the films and computer simulation of hydrated CuPc* were performed to substantiate an idea of colloidal MPc-water aggregates as nanoscale precursors of smooth solid films. This idea appears fruitful in terms of materials chemistry.     

Tetra- and Triarylantimony Fluorobenzoates: Synthesis and Structures

The reactions of pentaarylantimony (Ar₅Sb, where Ar = Ph or p-Tol) with triarylantimony bis(pentafluorobenzoate) and triarylantimony bis(3,4,5-trifluorobenzoate) in toluene afforded tetraarylantimony pentafluoro- and 3,4,5-trifluorobenzoates in up to 90% yields. The starting triarylantimony bis(pentafluorobenzoates) and bis(3,4,5-trifluorobenzoates) were prepared in ether by oxidative addition involving triarylstibine, hydrogen peroxide, and pentafluorobenzoic or 3,4,5-trifluorobenzoic acid, respectively, in up to 98% yields. Tetra-p-tolylantimony pentafluorobenzoate and triphenylantimony bis(pentafluorobenzoate) were structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with axial carboxy groups. In these compounds, the Sb atoms and carbonyl O atoms are linked by intramolecular contacts, which are especially pronounced in the latter complex (the Sb···O(=C) distances are 3.377(3) and 2.943(2), 3.167(2) Å, respectively).     

Tetra- and triarylantimony pentafluoroand pentachlorophenoxides: Synthesis and structure

2,3,4,5,6-Pentafluorophenoxytetraphenylantimony (I), 2,3,4,5,6-pentachlorophenoxytetraphenylantimony (_II), 2,3,4,5,6-pentafluorophenoxytetra-p-tolylantimony (III), and 2,3,4,5,6-pentachlorophenoxytetra-p-tolylantimony (IV) were synthesized by the reaction of pentaarylantimony (Ar = Ph, p-Tol) with pentafluoro- and pentachlorophenol in toluene. Compounds I–IV were also synthesized with yields of up to 95% from pentaarylantimony and triarylantimony diaroxides. Triarylantimony diaroxides Ph₃Sb(OC₆F₅)₂ (V), Ph₃Sb(OC₆Cl₅)₂ (VI), p-Tol₃Sb(OC₆F₅)₂ (VII), p-Tol₃Sb(OC₆Cl₅)₂ (VIII) were synthesized from triarylantimony, tert-butylhydroperoxide, and phenol in ether. The Sb atoms in compounds I–VIII had a distorted trigonal bipyramidal coordination with electronegative ligands in axial positions.     

两种甲氧基苯基咔咯铜配合物的合成及光谱性质

合成了两个中位苯基上具有甲氧基取代基的铜咔咯配合物(Tp-OCH3PC)Cu和(To,p-(OCH3)2PC)Cu,通过紫外-可见、红外光谱、元素分析、核磁共振及质谱对它们进行了表征。研究了配合物在非水溶剂中的电子顺磁共振、电化学和光谱电化学性质,结果表明无论在固体状态还是在非水溶剂中,配合物的中心金属离子均为三价铜Cu(Ⅲ),在给定的溶剂中Cu(Ⅲ)可以发生可逆的还原反应生成Cu(Ⅱ),也可以被可逆氧化为Cu(Ⅲ)的阳离子自由基。探讨了甲氧基取代基以及溶剂对配合物的紫外-可见光谱和氧化还原电位的影响。     

易溶性铜酞菁磺酸酯的合成及其凝聚性能

将酞菁氯磺化,然后与含有羟基的化合物反应,合成了铜酞菁磺酸苯酯、铜酞菁磺酸邻甲基苯酯、铜酞菁磺酸萘酯和铜酞菁磺酸 4 乙基萘酯,并测定了产物在不同溶剂中的溶解度、凝聚性能及红外光谱.这类铜酞菁衍生物的酯溶性很好.     

Synthesis and Properties of 4-Acyloxy-5-nitrophthalodinitriles and Copper(II) Phthalocyanines Derived Thereof

Acylation of 4-hydroxy-5-nitrophthalonitrile gave 4-acetoxy-5-nitro- and 4-benzoyloxy-5-nitrophthalonitriles. The products were reacted with copper(II) acetate to obtain the corresponding octasubstituted phthalocyanines.