Metal-Containing Phthalocyanines Substituted with One Branched Bulky Moiety and Six Alkylthio Groups

Summary.  Unsymmetrically substituted metal-phthalocyanines composed of three hexylthio groups and one 1-chloro-3,4-dicyano-6-[2-(2-pyridylmethylamino)phenylthio]benzene moiety was prepared by cyclization of the reactants in the presence of the anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The new unsymmetric phthalocyanines are very soluble in common organic solvents. The compounds were characterised by their elemental analyses, IR, ¹H NMR, MS and UV/Vis spectra. Corresponding author. E-mail: bayir@itu.edu.tr Received November 27, 2002; accepted (revised) December 2, 2002 Published online May 2, 2003     

Synthesis of New Metal-Free and Metal-Containing Phthalocyanines with Tertiaryor Quaternary Aminoethyl Substituents

Summary.  A novel phthalodinitrile derivative carrying dimethylaminoethylsulfanyl groups at positions 4 and 5 was synthesized from 2-dimethylaminoethanethiol hydrochloride and 1,2-dichloro-4,5-dicyanobenzene. Its cyclotetramerization in the presence of 2-dimethylamino-ethanol or metal salts (CoCl₂, Zn(OAc)₂) gave metal-free or metal-containing phthalocyanines (M = Co or Zn). These phthalocyanines were converted into water soluble quaternized products by reaction with methyl iodide. The new compounds were characterized by elemental analysis, IR, NMR, and electronic spectra.     

大基团取代不对称茂钛（Ⅳ）化合物的合成

大基团取代不对称茂钛（Ⅳ）化合物的合成舒学军贺峥杰＊陈寿山（南开大学元素有机化学研究所天津３０００７１）关键词有机锂，富烯，茂钛化合物，合成１９９６－０６－１９收稿，１９９６－１２－３１修回国家自然科学基金资助课题取代茂钛化合物常常是烯烃异构化的良好...     

New Phosphaalkenes with Alkylthio and Fluorenylidene Groups. Synthesis and Properties

Abstract

Synthesis and properties of new phosphaalkenes having different functional substituents at phosphorus and carbon atoms are discussed.     

Synthesis and Characterization of New Unsymmetrically Substituted Phthalocyanines

Summary.  Unsymmetric metallophthalocyanines (M=Zn, Co, Ni) carrying alkylthio and acetyloxyethylthio groups on peripheral positions were prepared from 4,5-bis-alkylthio-phthalonitrile, 4,5-bis-(acetyloxyethylthio)-phthalonitrile, and the corresponding anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The extremely soluble compounds were characterized by their IR, ¹H NMR, and UV/Vis spectra. Their long wavelength absorption band was found to be bathochromically shifted; their solubility is superior to that of symmetrical phthalocyanines. Received July 27, 1999. Accepted (revised) September 30, 1999     

取代锌酞菁的合成及光物理性质

取代锌酞菁的合成及光物理性质张先付,许慧君（中国科学院感光化学研究所,北京,１００１０１）关键词取代酞菁,合成,光物理性质,电荷转移癌症的光动力疗法及其机制是目前光医学、光生物学及光化学的前沿课题［１］。临床应用的光疗药物──血卟啉有一些难以克服的致...     

Synthesis and Characterization of New Unsymmetrically Substituted Phthalocyanines

 Unsymmetric metallophthalocyanines (M=Zn, Co, Ni) carrying alkylthio and acetyloxyethylthio groups on peripheral positions were prepared from 4,5-bis-alkylthio-phthalonitrile, 4,5-bis-(acetyloxyethylthio)-phthalonitrile, and the corresponding anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The extremely soluble compounds were characterized by their IR, ¹H NMR, and UV/Vis spectra. Their long wavelength absorption band was found to be bathochromically shifted; their solubility is superior to that of symmetrical phthalocyanines.     

The Synthesis of New Phthalocyanines Substituted with 12-Membered Diazadioxa Macrocycles

 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.     

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     

α-四(烷基苯氧基)酞菁配合物的合成与表征

以邻苯二甲酸酐为原料，经硝化、氨化、亲核取代和金属离子模扳等多步反应合成了两个系列共5个叔丁基取代苯氧基金属酞菁配合物，产物经元素分析，IR表征，测定了目标配合物的紫外可见吸收光谱、荧光光谱及在有机溶剂中的溶解性。结果发现：与无取代金属酞菁配合物相比，Q带最大吸收光谱波长红移；在710nm波激发下，目标配合物在环已烷等有机溶剂中均有荧光发射(最大发射波长在760nm左右)；在二氯甲烷、氯仿、环已烷、Py、苯、甲苯、乙基环已烷、乙基溶纤剂等中溶解性能良好。     

Nucleophilic Substitution of 4-Bromo-5-nitrophthalodinitrile: XVII. Synthesis and Properties of Bifunctionally Substituted Metal Phthalocyanines with Aryloxy and Nitro Groups

By substitution of bromine in 4-bromo-5-nitrophthalonitrile 4-(aryloxy)-5-nitrophthalonitriles were synthesized and, on their basis, cobalt and copper tetra(4-aryloxy-5-nitro)phthalo-cyanines were prepared. Spectral properties of the obtained octasubstituted phthalocyanines were investigated.     

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.     

Syntheses of Polythioethers Tethered with Bulky Aryl Groups and Their Complexation with Late-Transition Metals

Abstract

New types of o-phenylene-bridged polythioethers tethered with extremely bulky aryl groups at their terminal sulfur atoms, such as TbtS(o-Phen)S(o-Phen)S(o-Phen)STbt (1) and TbtS(o-Phen)S(o-Phen)SS(o-Phen)S(o-Phen)STbt (2) (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, o-Phen = o-phenylene), were synthesized and subjected to the complexation with several kinds of late-transition metals. In the case of polythioether 1, the reaction with RhCl₃·3H₂O in benzene/EtOH resulted in the formation of a unique bimetallic complex, in which a part of ligand 1 is lost and the resulting sulfur atom is directly bound to the other Rh metal center. Interestingly, similar treatment of 1 with IrCl₃·3H₂O afforded ethyl-coordinated mononuclear Ir complex. Furthermore, 1 underwent complexation with Na₂PdCl₄ in EtOH to give the corresponding square planar dichloropalladium complex coordinated with two inner sulfur atoms of 1, while the S₆-ligand 2 reacted with excess of Pd(PPh₃)₄ in benzene to afford a quite interesting trinuclear Pd complex multi-step metal insertion reactions.     

单冠醚取代不对称酞菁LB膜的制备和表征

酞菁化合物有序聚集体已成为材料化学中的研究热点［１,２］,在酞菁分子中引入冠醚会大大改善酞菁化合物的气敏性,在提高响应速度和重复性的同时,其响应温度可降到室温［３,４］．研究冠醚酞菁气敏性质的通常方法是将其制成浇铸膜［４］,这种膜是无序的．膜中分子的...     

中氮茚腈类化合物的合成及其荧光性质的研究

合成了一系列中氮茚化合物,研究了化合物3a～3k,4a～4b,5～6分子中不同取代基对其荧光光谱和荧光量子效率的影响.发现中氮茚环上的氰基具有较好的荧光助色作用,中氮茚环上的COPh,COMe或CHO对分子的荧光具有猝灭作用;发现中氮茚类有机化合物的分子结构与荧光性质之间的某些关系.化合物3a～3b,3g～3i具有较高的荧光量子效率,可以作为比较好的有机荧光分子用于探针化合物的结构修饰.     

Synthesis and Spectral-Luminescent Properties of Octa-substituted Aluminum Phthalocyanines Bearing Biphenyloxy Groups

Russian Journal of General Chemistry - Mixed-substituted aluminum phthalocyanines bearing biphenyloxy substituents and nitro groups or 1-benzotriazole moieties in the periphery were synthesized on...     

均三嗪含氮取代基衍生物的结构和性质

在B3LYP/aug-cc-pvDZ理论水平上研究了—CN、—NO2、—NH2、—N3 、—N2H、—NHNH2、—N4H和—N4H3等含氮取代基取代均三嗪环上的氢原子生成的衍生物, 预测了它们的分子构型、分解能及含能性质. 对衍生物分解能的研究结果表明, —CN 和—NH2取代的衍生物的分解能比未取代时更高, 而其余基团的取代使分解能降低; 取代基化合物的生成热越大, 取代均三嗪中的氢原子后生成衍生物的生成热也越大. —CN、—N3和—N4H取代的均三嗪衍生物的单位原子生成热为71.9、78.7 和82.6 kJ, 比文献报道的三叠氮基-均三嗪的(70.2 kJ)更高. —N4H、—N3 、—N4 H3 、—N2 H和—CN取代的均三嗪衍生物, 生成热为863.1-1735.2 kJ·mol-1, 但—N4H和—N4H3取代的衍生物分解能较小,稳定性较差.     

A Common Conformation of Stabilized Triphenyl Phosphonium Ylidic Diesters with Bulky Alkoxy Groups

The phosphonium ylidic diesters, methyl and ethyl isopropyl and, methyl and ethyl t-butyl triphenylphosphoranylidene malonates, 1a,b and 2a,b , respectively, have the syn-anti conformation in solution, as in the crystal, and the bulkier alkoxy group is oriented towards phosphorus. The ¹ H NMR spectra show that in 1a,b , the isopropyl group is oriented towards the face of a phenyl group, consistent with π shielding in the ¹ H signals, and examination of the ¹ H coupled ¹³ C NMR spectra allows assignment of the acyl carbon signals. Computed bond lengths and angles for isolated molecules are similar to those in the crystal, and the geometry and the NMR spectra indicate extensive ylidic resonance. Estimated partial atomic charges on the ester oxygens are more negative when they are oriented towards, rather than away from, phosphorus.