取代金属酞菁的合成及其性质
|
摘要
酞菁类化合物具有高度共轭的π电子体系，由于大环体系间强的电子相互作用，在可见区有强的跃迁，使该类化合物显示出独特的光、电、热、磁的性质，酞菁类化合物作为一种功能性材料，由于它所具有的独特的物理、化学性能，因此被广泛应用于高科技领域，受到世界各国研究人员的普遍关注。
本文从邻苯二甲酸酐出发合成了十二个取代邻苯二腈，用这些取代邻苯二腈化合物合成了四个取代金属及空心酞菁，以4-硝基邻苯二甲酰亚胺和金属卤化物为原料，一步合成了2，9，16，23-四硝基金属酞菁，还原后得到2，9，16，23-四氨基金属酞菁，同时以2，9，16，23-四氨基金属酞菁、对苯二胺和1，2，4-苯三酸酐为原料，合成了含酞菁结构的聚合物。
测定了十二个取代邻苯二腈的红外光谱、紫外光谱、核磁共振谱；研究了酚类化合物与4-硝基邻苯二腈的反应，结果表明，取代酚的苯环上连有推电子基有利于反应进行，而连有拉电子基使反应减慢甚至不反应。
测定了取代金属酞菁的红外光谱、紫外光谱、质谱；研究了影响酞菁紫外光谱的因素，结果表明，(1)芳氧取代基使酞菁的Q带红移；(2)金属离子的引入使酞菁的Q带蓝移，蓝移大小顺序为Ni(Ⅱ)＞Co(Ⅱ)＞Zn(Ⅱ)＞Mn(Ⅱ)＞Cu(Ⅱ)＞Fe(Ⅱ)；(3)不同溶剂中酞菁Q带吸收峰位置不同；测定了含酞菁结构聚合物的热失重，结果表明，聚合物的耐热温度明显高于单体酞菁。
用量子化学EHMO/CO方法研究了四氨基金属酞菁的能带结构，讨论了不同金属酞菁的能带结构，结果表明，氨基钴酞菁的带隙最小，而氨基镍酞菁的带隙最大。
Phthalocyanine compounds with their 18-electronic delocalization of intense electronic interction in macrocycle and intense transition in visible region display peculiar photo-electricall, thermal and magnetic characters. As molecular-functional materials, compounds of phthalocyAnine with peculiar physical and chemical properties which are widely used in advanceded science and technology field, has attracted more and more interest of chemists and physicists in the world.
In this paper, dozen 4-substituted-1,2 dicyanobenzenes of preceding compounds of substituted phthalocyanine were synthesized through phthalic anhydride, then four substituent metal and free-metal phthalocyanine compounds were synthesized using these substituted dicyanobenzene. A simple method was applying in the synthesis of 2,9,16,23-tetranitrometal phthalocyanine, 4-nitrophthalimide and metallic halide were using as essential material in this reaction, by reducing, 2,9,16,23-teraamino-metal phthalocyanine were obtained. We synthesized polymer which included phthalocyanine structure with 2,9,16,23-tetraaminometal phthalocyanine p-phenylenediamine and benzol-1,2,4-tricarbonsaure-1,2-anhydrid.
These substituted dicyanobenzene compounds were also characterized with IR, UV-Vis and 1HNMR methods; The reaction of phthaleins and 4-nitro-1,2 dicyanobenzene was investigated, the result showed, it was propitious to the reaction when donor groups were linked in the phthaleins, but the reaction became slower and even the reaction did not take place when electron withdrawing group existed.
Substituent metal and free-metal phthalocyanine compounds were characterized with IR, UV-Vis and MS methods, the results showed, (1) aryloxy resulted red shift in Q absorption band of phthalocyanine; (2) metal ion resulted blue shift in Q absorption band, sequence was Ni>Co>Zn>Mn>Cu>Fe; (3) absorption position was different hi different solvents; thermogravimetric analysis showed that heat resistant temperature of polymer was higher than monomer phthalocyanine
obviously.
Band structure of teraamino-metal phthalocyanine was studied through EHMO/CO method, band structure of different metal phthalocyanine was discussed, the result showed that band gap of teraamino-cobalt phthalocyanine was smallest, while band gap of teraamino-nickel phthalocyanine was biggest.
本文从邻苯二甲酸酐出发合成了十二个取代邻苯二腈，用这些取代邻苯二腈化合物合成了四个取代金属及空心酞菁，以4-硝基邻苯二甲酰亚胺和金属卤化物为原料，一步合成了2，9，16，23-四硝基金属酞菁，还原后得到2，9，16，23-四氨基金属酞菁，同时以2，9，16，23-四氨基金属酞菁、对苯二胺和1，2，4-苯三酸酐为原料，合成了含酞菁结构的聚合物。
测定了十二个取代邻苯二腈的红外光谱、紫外光谱、核磁共振谱；研究了酚类化合物与4-硝基邻苯二腈的反应，结果表明，取代酚的苯环上连有推电子基有利于反应进行，而连有拉电子基使反应减慢甚至不反应。
测定了取代金属酞菁的红外光谱、紫外光谱、质谱；研究了影响酞菁紫外光谱的因素，结果表明，(1)芳氧取代基使酞菁的Q带红移；(2)金属离子的引入使酞菁的Q带蓝移，蓝移大小顺序为Ni(Ⅱ)＞Co(Ⅱ)＞Zn(Ⅱ)＞Mn(Ⅱ)＞Cu(Ⅱ)＞Fe(Ⅱ)；(3)不同溶剂中酞菁Q带吸收峰位置不同；测定了含酞菁结构聚合物的热失重，结果表明，聚合物的耐热温度明显高于单体酞菁。
用量子化学EHMO/CO方法研究了四氨基金属酞菁的能带结构，讨论了不同金属酞菁的能带结构，结果表明，氨基钴酞菁的带隙最小，而氨基镍酞菁的带隙最大。
Phthalocyanine compounds with their 18-electronic delocalization of intense electronic interction in macrocycle and intense transition in visible region display peculiar photo-electricall, thermal and magnetic characters. As molecular-functional materials, compounds of phthalocyAnine with peculiar physical and chemical properties which are widely used in advanceded science and technology field, has attracted more and more interest of chemists and physicists in the world.
In this paper, dozen 4-substituted-1,2 dicyanobenzenes of preceding compounds of substituted phthalocyanine were synthesized through phthalic anhydride, then four substituent metal and free-metal phthalocyanine compounds were synthesized using these substituted dicyanobenzene. A simple method was applying in the synthesis of 2,9,16,23-tetranitrometal phthalocyanine, 4-nitrophthalimide and metallic halide were using as essential material in this reaction, by reducing, 2,9,16,23-teraamino-metal phthalocyanine were obtained. We synthesized polymer which included phthalocyanine structure with 2,9,16,23-tetraaminometal phthalocyanine p-phenylenediamine and benzol-1,2,4-tricarbonsaure-1,2-anhydrid.
These substituted dicyanobenzene compounds were also characterized with IR, UV-Vis and 1HNMR methods; The reaction of phthaleins and 4-nitro-1,2 dicyanobenzene was investigated, the result showed, it was propitious to the reaction when donor groups were linked in the phthaleins, but the reaction became slower and even the reaction did not take place when electron withdrawing group existed.
Substituent metal and free-metal phthalocyanine compounds were characterized with IR, UV-Vis and MS methods, the results showed, (1) aryloxy resulted red shift in Q absorption band of phthalocyanine; (2) metal ion resulted blue shift in Q absorption band, sequence was Ni>Co>Zn>Mn>Cu>Fe; (3) absorption position was different hi different solvents; thermogravimetric analysis showed that heat resistant temperature of polymer was higher than monomer phthalocyanine
obviously.
Band structure of teraamino-metal phthalocyanine was studied through EHMO/CO method, band structure of different metal phthalocyanine was discussed, the result showed that band gap of teraamino-cobalt phthalocyanine was smallest, while band gap of teraamino-nickel phthalocyanine was biggest.
引文
[1] Braun A., Tchemiac J., Chem. Ber. 1907, 40:2709
[2] de Diesbach H, Schmidt V, Decker E. Helv. Chim. Acta. 1923, 6:548
[3] de Diesbach H, von der Weidd E. Helv. Chim. Acta. 1927, 10:886
[4] Moser F H, Thomas A L. Phthalocyanine. New York: Reinhold Publishing Corporation, 1963.3
[5] R. P. Linstead, J. M. Robertson. An X-Ray Study of the Phthalocyanines. Part Ⅱ. Quantitative Structure Determination of the Metal-free Compound. J. Chem. Soc. 1936, 1195-1198
[6] R.L. Jone.and R. P. Linstead. Fused Carbon Rings. Part Ⅺ. The Action of Aluminium Chloride on Decalin. J. Chem. Soc. 1936, 615-621
[7] M. Hanach, M. Lang; Conducting Stacked Metallophthalocyanines and Related Compounds. Adv. Mater. 1994, 6:819-833
[8] 沈永嘉等 酞菁的合成与应用 化学工业出版社 2000年2月第一版
[9] Lever A B P. The other periodic chart. CHEMTECH. 1987,8:506
[10] 陈元胜、许志康、朱宝库、徐又一．光电导性聚酰亚胺的研究(Ⅰ)-含咔唑酞菁铜聚酰亚胺的合成与表征及其光电导性能研究．高等学校化学学报．1997，18(6)：973
[11] Chen H Z, Wang M Yang S L, Synthesis and Photoconductivity Study of Phthalocyanine Polymers. V.4,4'-Diamino-diphenyl Ether Bridged Polymeric SiPc J. Polym. Sci A: Polym. Chem. 1997, 35 (9): 1-95
[12] De Quan Li, M. Lutt, M. R. Fitzsimmons, R. Synowicki, M. E. Hawley, and G.W. Brown. Preparation, Characterization, and Properties of Mixed Organic and Polymeric Self-Assembled Multilayers. J. Am. Chem. Soc. 1998, 120:8797-8804
[13] Shafrira Greenberg, Sebastian M. Marcuccio, Clifford C. Leznoff, Seletive Synthesis of Binuclear and Trinuclear Phatahlocuyannies Covalently Linked by a One Atom Oxygen Bridge Synthesis 1986, 406-409
[14] Clifford C.:Leznoff, Polina I. Svirskaya, Ben Khouw; Syntheses of monometalated and unsymmetrially substituted bisclear phthalocy-anines and pentanuclear phthalocyanine by solution and polymer support methods. J. Org. Chem. 1991, 56:82-90
[15] Wheeler B. L., Nagasubramanian G. Bard A. J.; A silicon phthalocy-anine and silicon naphthalocyanine synthesis, electrochemistry and electrogenerated chemiluminescene. J. Am. Chem. Soc. 1984, 106: 7404-7410
[16] Herman Lam, Sebastian M. Marcuccio, Polina Ⅰ. Svirskaya; Binuclear phthalocyanines with aromatic bridges. Can. J. Chem. 1989,67:1087-1097
[17] 石鑫．氨基取代酞菁及其前体化合物的合成、表征和酞菁成环机理以及荧光性质的研究．[硕士学位论文] 长春，东北师范大学 2001
[18] M. A. A B D EL-Chaffar; Electric studies or some metal biphthacy-anine complexes. Thermochimica Acta. 1991, 178:257-262
[19] Jiang Yang and Michael Van De Mark; Synthesis of binuclear phthalocyanines sharing a benzene or naphthalene ring. Tetrahedron Lett. 1993, 34:5223-5226
[20] E. Elshereafy and M. A. Abd EL-Ghaffar; Eletrical and thermal studies on copper complexes of phthalocyanine and biphthalocyanine and their derivatives. Thermochimica Acta. 1991, 186:179-185
[21] F. H. Moser, A. L. Thomas, "Phthalocyanine Compounds", 2ed Edition. Reinhold, New York, 1983
[22] B Y C. S. Marvel and John H. Rassweller. Polymer Phthalocyanines. J. Am. Chem. Soc., 1958, 80:1197-1199
[23] Hirofusa Shiral, Akio Maruyama, Kesayoshi Kobayashi, Nobumasa Hojo. Functional metal-porphyrazine derivatives and their polymers4~(a))Synthesis of Poly(styrene) bonded Fe(Ⅲ)-as well as Co(Ⅱ)-4,4',4",
4'"-tetracarboxyphthalocyanine and Their Catalase-like Activity. Makromol. Chem., 1980, 181:575-584
[24] Hirofusa Shirai, Sadafumi Yagi, Aldra Suzuki, and Nobumasa Hojo Functional metal-porphyrazine derivatives and their polymers, 1 Synthesis of Metal-[2,9or 10(or2,16or17)bis(3,4-dicarboxybenzoyl)] phthalocyanine Derivatives. Makromol. Chem.,1977,178:1889-1895
[25] D. Wohrle, et al., Makromol. Chem., 1985, 186:2209
[26] Dieter Wohrle, Gerhard Krawczyk. Polymeric bound porphyines and their precursors, 3~(a)) photoredox properties of combined moieties of porphyrine and phthalocyanine, covalently bound to polystyrene. Makromol. Chem., 1986, 187:2535
[27] D. Wohrle, et al., Makromol. Chem., 1986, 187:2947
[28] Hirofusa Shirai, Kesayoshi Kobayashi, Yoshitaka Takemae,Akira Suzuki, Okikazu Hirabaru, and Nobumasa Hojo.Functional Metal-porphyrazine Derivatives and Their Polymer, 2~(a)) Synthesis and Properties of Polyimides Containing Metal-phthalocyanines Makromol. Chem. 1979, 180:2073
[29] S. Morris Kupchan, Chang Kyu Kim, and J. Thomas. Lynn. Biomimetic Synthesis of a Key Erythrina Alkaloid Precursor. J. Chem. Soc. Chem. Commun., 1976, 86-88
[30] Hirofusa Shirai, Yoshitaka Takemae, Kesayoshi Kobayashi, Yoshiyuki Kondo, Okikazu Hirabam, Nobumasa Hojo. Functional metal-porphyrazine derivatives and their polymers, 12~(a)) Synthesis and properties of polyimides containing a metal-phthalocyanine ring and apyridyl group. Makromol. Chem. 1984, 185:1395-1401
[31] B. N. ACHAR, G. M. FOHLEN, and J. A. PARKER. Phthalocy-anine Polymers .I. Poly[2,2'-(4,4',4",4'"-MetalPhthalocyanino)-5,5' -Bibenzimidazoles] as New High Temperature Resistant Polymers. J. Polym. Sci., Polym. Chemistry. Edition, 1982, 20:269-275
[32] M. Gebler, J. Inorg. Nucl. Chem., 1981, 43:2759
[33] Dieter Wohrle and Gerhard Krawczyk. Polymeric Bound Porphyrines and Their Precursors 2. Solid Phase Synthesis of a Monosubstitued Phthalocyanine. Polym. Bull. 1986, 15:193-200
[34] Otto Schneider, and Michael Hanack. Phthalocyaninatoiron with Pyrazine as a Bidentate Bridging Ligand. Angew. Chem. Int. Ed. Engl., 1980, 19:392-393
[35] K. Fischer, M, H.anack, Chem. Ber., 1983, 116:1860
[36] Byrne A, Linstead R P, Phthalocyanines Part. Ⅱ. The preparation of phthalocyanine and some Metallic Derivatives from o-cyanobenz-amide and phthalimide. J. Chem. Soc. 1934, 1017
[37] Metz J, Schmeider O; Inorg. Chem. 1984, 23:1065
[38] 杨树卿等 中国发明专利 ZL85．1．089320．1，1985
[39] Brach P J, Grammatica S J; J. Hetero. Chem. 1970, 7:1403
[40] Barrett P A, Frye D A, Linstead R P. Phthalocyanines and Associated Compounds. Part. ⅩⅣ. Further Investigations of Metallic Derivatives. J. Chem. Soc. 1938:1157
[41] NagaoKobayashi, Herman Lam, W. Andrew Nevin; Synthesis, spectroscopy, electrochemistry, spectroeletrochemistry, Langmuir-Blodgett of planar binuclear phthalocyanines. J. Am. Chem. Soc. 1994, 116:879-890
[42] C. C. Leznoff, S. Greenberg, S. M. Marcuccio, Binuclear Clamshell Metallophthalocyanines. Inorg. Chem. Acta. 1984, 89:L35-L38
[43] Lezenoff C C, Hall W. The Synthesis of a Soluble Unsymmetrical. Phthalocyanine on a Polymer Support. Tetrahedron Lett. 1982, 23: 3023-3027
[44] Hall T W, Greenberg S, McArthur C R, Khouw B, Lezenoff C C. Nouv. J. Chim. 1982, 6:653
[45] Shaferira Greenberg, A.B P. Lever, and Clifford C. Lezenoff. Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pnreisomer. Can. J. Chem. 1988, 66:1059
[46] Ficken G E, Linstead R P, Stephen E, Whalley M. Conjugated Macrocycles. Part. ⅩⅩⅪ. Catalytic Hydrogenation of Tetrazaporphins with a Note on its Stereochemical Course. J. Chem. Soc. 1958:3879
[47] Wyler. M, GB 457786 1936
[48] Vollmam H, Baumann F, Bienent B; US 2701252 1955
[49] Gaspard S, Maillard Ph. Tetrahedron. 1987, 43:1083
[50] 杨树卿，陈彬，杜锡光；双核酞菁钴磺酸盐催化脱硫机理研究催化学报 1993，14：No．2 150-154
[51] Ichikawa M. Japan Kokai, JP 74116010, 1974
[52] 孙强，房兆龄，苏永成等 金属酞菁对碘苯的乙烯化反应的催化研究．东北师范大学学报 1995，3：56-60
[53] 李雪萍，于大勇，韩晓祥等 金属酞菁催化苯乙烯液相氧化反应石油化工高等学校学报 1995，11：No．4 21-24
[54] Nagew Kobayashi, Hidaya Miwa. Inorg. Chem. 1999, 38:479
[55] D. F. Barbe, C.R. Westgate. J. Phys. Chem. Solids 1970, 31:2679
[56] Dennis K. P. Ng snd Jianzhuang Jiang Sandwich-type heteroleptic phthalocyaninato and porphyrinato metal complexes. Chemical Society Reviews. 1997, 26:433-442
[57] Yong-Le Pan, Ling-Bing Che, Yan Wang. Appl. Phys. Lett 1996, 68: 1314
[58] J. W. Perry, K. Mansour, 1.-Y. S. Lee, X.-L. Wu, P. V. Bedworth, C.-T. Chen, D.Ng, S. R. Marder, P. Miles, T. Wada, M. T. ian, H. Sasabe. SCIENCE. 1996, 273:1533-1536
[59] Takeo Tomiyama, Ltsuo Watanabe, Atsushi Kuwano, Masanobu Habiro, Nobuaki Takane, and Mitsuo Yamada. Rewritable optical-disk fabrication with an optical recording material made of naphthalocyaning and polythiophene. Appl. Optics. 1995, 34:8201-8208
[60] 吴永忠．取代酞菁的光电性能研究[学位论文]．上海：华东理工大学，1996
[61] Achar B N,Fohlen G M and Parker. Heat-Resistant Poly(metal,Phtha-locyanine)imide Coplymers using Benzenetetracar-boxylic Dianhy-dride. J.A.J. Poly. Sci. Chem Ed 1985, 23 (3): 801-811
[62] Achar B N,Fohlen G M and Parker. Novel High-Temperature-Resis-tant Metal Phthalocyanine Imide Copolymers. J A. J. Poly. Sci. Chem Ed 1983, 21:3063-3072
[63] 刘宝殿，张耀刚：有机合成化学实验 邻苯二甲酰胺的合成30
[64] Joseph G.Young, William Onyebuagu; Synthesis and Characterri-
zation of Di-disubstituted phthalocyanine. J. Org. Chem. 1990, 55: 2155
[65] John Griffiths, Bizhan Roozpeikar; Synthesis and electronic absorption spectra of dicyano-deribative of 4-diethylaminoabenzene. J.C.S. Perkin I 1976, 42
[66] Han, Jiang hua; Bai, Bao lin; Zhao, Ming gen. Synthesis of schiff bases of digoethylene glyco bridged disalicylic aldehydes with anthranilic acid schiff base. Hua xue shi ji. 1995, 17 (6): 363-364
[67] 樊能延编著 有机合成事典。北京理工大学出版社
[68] Clifford C. Leznoff and Neil B. Mckeown Prepartion of Substituted Tetrabenzotriazaporphyrins and a Tetranaphthatriaza-porphyrin: A Route to Mono-meso-substituted Phthalocyanine Analogues J. Org. Chem. 1990,55:2186-2190
[69] Paul J. Brach, steven J. Grammatica, Oliver A Ossacha and Lester Weinberger. Improved Sythesis of metal-free phthalocyanine Webster, New York 14580
[70] Andreas Gouloumis, Shen-Gao Liu, Angela Sastre, Parificacion Vazquez, Luis Echegoyen and Torres Sythesis and Electrochemical Preperties of Pthalocyanine-Fullerene Hybrids. Chem. Eur. J 2000, 19:3600-3607
[71] 张先付、许慧君．取代锌酞菁的合成及光物理性质．高等学校化学学报 1994，6：917-919
[72] Achar B N, Fohlen G M and Parker. ?hthalocyanine Polymers Ⅳ. Novel Type of Thermally Stable Polyimides Derived From Metal Phthalocyanine Tetramines and Benzophenone Dianhydride. J. A. J. Poly. Sci. Chem Ed, 1982, 20:2773-2780
[73] Achar B N, Fohlen G M and Parker. Heat-Resistant Metal Phthalocyanine Imide Copolymers. J.A.J. Poly. Sci. Chem Ed, 1983, 21:1025-1032
[74] 赵剑波，赵福群，赵瑜，张复实等．空心酞菁光物理性质的取代基效应(英文) 物理化学学报 1996，12(6)：491-495
[75] Bredas, O.P. Chem. Mater. 1990, 2:110
[76] E. Elshereafy and M. A. Abd EL-Ghaffar; Eletrical and thermal studies on copper complexes of phthalocyanine and biphthalocyanine and their derivatives. Thermochimica Acta. 1991, 186:179-185
[77] 詹梦雄，郑标练，顾学民．厦门大学学报自然科学版．1986，25(2)：192-198
[78] K Burger. Coordination Chemistry, Experimental methods. London 1973, 8:315-334
[79] Lobayashi. N. M, Lever A. B.P.; Cation-or solvent-induced super-molecular phthalocyanine formation: crown ether substituted phthalocyanine. J. Am. Chem. Soc. 1987, 109:7433-7441
[2] de Diesbach H, Schmidt V, Decker E. Helv. Chim. Acta. 1923, 6:548
[3] de Diesbach H, von der Weidd E. Helv. Chim. Acta. 1927, 10:886
[4] Moser F H, Thomas A L. Phthalocyanine. New York: Reinhold Publishing Corporation, 1963.3
[5] R. P. Linstead, J. M. Robertson. An X-Ray Study of the Phthalocyanines. Part Ⅱ. Quantitative Structure Determination of the Metal-free Compound. J. Chem. Soc. 1936, 1195-1198
[6] R.L. Jone.and R. P. Linstead. Fused Carbon Rings. Part Ⅺ. The Action of Aluminium Chloride on Decalin. J. Chem. Soc. 1936, 615-621
[7] M. Hanach, M. Lang; Conducting Stacked Metallophthalocyanines and Related Compounds. Adv. Mater. 1994, 6:819-833
[8] 沈永嘉等 酞菁的合成与应用 化学工业出版社 2000年2月第一版
[9] Lever A B P. The other periodic chart. CHEMTECH. 1987,8:506
[10] 陈元胜、许志康、朱宝库、徐又一．光电导性聚酰亚胺的研究(Ⅰ)-含咔唑酞菁铜聚酰亚胺的合成与表征及其光电导性能研究．高等学校化学学报．1997，18(6)：973
[11] Chen H Z, Wang M Yang S L, Synthesis and Photoconductivity Study of Phthalocyanine Polymers. V.4,4'-Diamino-diphenyl Ether Bridged Polymeric SiPc J. Polym. Sci A: Polym. Chem. 1997, 35 (9): 1-95
[12] De Quan Li, M. Lutt, M. R. Fitzsimmons, R. Synowicki, M. E. Hawley, and G.W. Brown. Preparation, Characterization, and Properties of Mixed Organic and Polymeric Self-Assembled Multilayers. J. Am. Chem. Soc. 1998, 120:8797-8804
[13] Shafrira Greenberg, Sebastian M. Marcuccio, Clifford C. Leznoff, Seletive Synthesis of Binuclear and Trinuclear Phatahlocuyannies Covalently Linked by a One Atom Oxygen Bridge Synthesis 1986, 406-409
[14] Clifford C.:Leznoff, Polina I. Svirskaya, Ben Khouw; Syntheses of monometalated and unsymmetrially substituted bisclear phthalocy-anines and pentanuclear phthalocyanine by solution and polymer support methods. J. Org. Chem. 1991, 56:82-90
[15] Wheeler B. L., Nagasubramanian G. Bard A. J.; A silicon phthalocy-anine and silicon naphthalocyanine synthesis, electrochemistry and electrogenerated chemiluminescene. J. Am. Chem. Soc. 1984, 106: 7404-7410
[16] Herman Lam, Sebastian M. Marcuccio, Polina Ⅰ. Svirskaya; Binuclear phthalocyanines with aromatic bridges. Can. J. Chem. 1989,67:1087-1097
[17] 石鑫．氨基取代酞菁及其前体化合物的合成、表征和酞菁成环机理以及荧光性质的研究．[硕士学位论文] 长春，东北师范大学 2001
[18] M. A. A B D EL-Chaffar; Electric studies or some metal biphthacy-anine complexes. Thermochimica Acta. 1991, 178:257-262
[19] Jiang Yang and Michael Van De Mark; Synthesis of binuclear phthalocyanines sharing a benzene or naphthalene ring. Tetrahedron Lett. 1993, 34:5223-5226
[20] E. Elshereafy and M. A. Abd EL-Ghaffar; Eletrical and thermal studies on copper complexes of phthalocyanine and biphthalocyanine and their derivatives. Thermochimica Acta. 1991, 186:179-185
[21] F. H. Moser, A. L. Thomas, "Phthalocyanine Compounds", 2ed Edition. Reinhold, New York, 1983
[22] B Y C. S. Marvel and John H. Rassweller. Polymer Phthalocyanines. J. Am. Chem. Soc., 1958, 80:1197-1199
[23] Hirofusa Shiral, Akio Maruyama, Kesayoshi Kobayashi, Nobumasa Hojo. Functional metal-porphyrazine derivatives and their polymers4~(a))Synthesis of Poly(styrene) bonded Fe(Ⅲ)-as well as Co(Ⅱ)-4,4',4",
4'"-tetracarboxyphthalocyanine and Their Catalase-like Activity. Makromol. Chem., 1980, 181:575-584
[24] Hirofusa Shirai, Sadafumi Yagi, Aldra Suzuki, and Nobumasa Hojo Functional metal-porphyrazine derivatives and their polymers, 1 Synthesis of Metal-[2,9or 10(or2,16or17)bis(3,4-dicarboxybenzoyl)] phthalocyanine Derivatives. Makromol. Chem.,1977,178:1889-1895
[25] D. Wohrle, et al., Makromol. Chem., 1985, 186:2209
[26] Dieter Wohrle, Gerhard Krawczyk. Polymeric bound porphyines and their precursors, 3~(a)) photoredox properties of combined moieties of porphyrine and phthalocyanine, covalently bound to polystyrene. Makromol. Chem., 1986, 187:2535
[27] D. Wohrle, et al., Makromol. Chem., 1986, 187:2947
[28] Hirofusa Shirai, Kesayoshi Kobayashi, Yoshitaka Takemae,Akira Suzuki, Okikazu Hirabaru, and Nobumasa Hojo.Functional Metal-porphyrazine Derivatives and Their Polymer, 2~(a)) Synthesis and Properties of Polyimides Containing Metal-phthalocyanines Makromol. Chem. 1979, 180:2073
[29] S. Morris Kupchan, Chang Kyu Kim, and J. Thomas. Lynn. Biomimetic Synthesis of a Key Erythrina Alkaloid Precursor. J. Chem. Soc. Chem. Commun., 1976, 86-88
[30] Hirofusa Shirai, Yoshitaka Takemae, Kesayoshi Kobayashi, Yoshiyuki Kondo, Okikazu Hirabam, Nobumasa Hojo. Functional metal-porphyrazine derivatives and their polymers, 12~(a)) Synthesis and properties of polyimides containing a metal-phthalocyanine ring and apyridyl group. Makromol. Chem. 1984, 185:1395-1401
[31] B. N. ACHAR, G. M. FOHLEN, and J. A. PARKER. Phthalocy-anine Polymers .I. Poly[2,2'-(4,4',4",4'"-MetalPhthalocyanino)-5,5' -Bibenzimidazoles] as New High Temperature Resistant Polymers. J. Polym. Sci., Polym. Chemistry. Edition, 1982, 20:269-275
[32] M. Gebler, J. Inorg. Nucl. Chem., 1981, 43:2759
[33] Dieter Wohrle and Gerhard Krawczyk. Polymeric Bound Porphyrines and Their Precursors 2. Solid Phase Synthesis of a Monosubstitued Phthalocyanine. Polym. Bull. 1986, 15:193-200
[34] Otto Schneider, and Michael Hanack. Phthalocyaninatoiron with Pyrazine as a Bidentate Bridging Ligand. Angew. Chem. Int. Ed. Engl., 1980, 19:392-393
[35] K. Fischer, M, H.anack, Chem. Ber., 1983, 116:1860
[36] Byrne A, Linstead R P, Phthalocyanines Part. Ⅱ. The preparation of phthalocyanine and some Metallic Derivatives from o-cyanobenz-amide and phthalimide. J. Chem. Soc. 1934, 1017
[37] Metz J, Schmeider O; Inorg. Chem. 1984, 23:1065
[38] 杨树卿等 中国发明专利 ZL85．1．089320．1，1985
[39] Brach P J, Grammatica S J; J. Hetero. Chem. 1970, 7:1403
[40] Barrett P A, Frye D A, Linstead R P. Phthalocyanines and Associated Compounds. Part. ⅩⅣ. Further Investigations of Metallic Derivatives. J. Chem. Soc. 1938:1157
[41] NagaoKobayashi, Herman Lam, W. Andrew Nevin; Synthesis, spectroscopy, electrochemistry, spectroeletrochemistry, Langmuir-Blodgett of planar binuclear phthalocyanines. J. Am. Chem. Soc. 1994, 116:879-890
[42] C. C. Leznoff, S. Greenberg, S. M. Marcuccio, Binuclear Clamshell Metallophthalocyanines. Inorg. Chem. Acta. 1984, 89:L35-L38
[43] Lezenoff C C, Hall W. The Synthesis of a Soluble Unsymmetrical. Phthalocyanine on a Polymer Support. Tetrahedron Lett. 1982, 23: 3023-3027
[44] Hall T W, Greenberg S, McArthur C R, Khouw B, Lezenoff C C. Nouv. J. Chim. 1982, 6:653
[45] Shaferira Greenberg, A.B P. Lever, and Clifford C. Lezenoff. Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pnreisomer. Can. J. Chem. 1988, 66:1059
[46] Ficken G E, Linstead R P, Stephen E, Whalley M. Conjugated Macrocycles. Part. ⅩⅩⅪ. Catalytic Hydrogenation of Tetrazaporphins with a Note on its Stereochemical Course. J. Chem. Soc. 1958:3879
[47] Wyler. M, GB 457786 1936
[48] Vollmam H, Baumann F, Bienent B; US 2701252 1955
[49] Gaspard S, Maillard Ph. Tetrahedron. 1987, 43:1083
[50] 杨树卿，陈彬，杜锡光；双核酞菁钴磺酸盐催化脱硫机理研究催化学报 1993，14：No．2 150-154
[51] Ichikawa M. Japan Kokai, JP 74116010, 1974
[52] 孙强，房兆龄，苏永成等 金属酞菁对碘苯的乙烯化反应的催化研究．东北师范大学学报 1995，3：56-60
[53] 李雪萍，于大勇，韩晓祥等 金属酞菁催化苯乙烯液相氧化反应石油化工高等学校学报 1995，11：No．4 21-24
[54] Nagew Kobayashi, Hidaya Miwa. Inorg. Chem. 1999, 38:479
[55] D. F. Barbe, C.R. Westgate. J. Phys. Chem. Solids 1970, 31:2679
[56] Dennis K. P. Ng snd Jianzhuang Jiang Sandwich-type heteroleptic phthalocyaninato and porphyrinato metal complexes. Chemical Society Reviews. 1997, 26:433-442
[57] Yong-Le Pan, Ling-Bing Che, Yan Wang. Appl. Phys. Lett 1996, 68: 1314
[58] J. W. Perry, K. Mansour, 1.-Y. S. Lee, X.-L. Wu, P. V. Bedworth, C.-T. Chen, D.Ng, S. R. Marder, P. Miles, T. Wada, M. T. ian, H. Sasabe. SCIENCE. 1996, 273:1533-1536
[59] Takeo Tomiyama, Ltsuo Watanabe, Atsushi Kuwano, Masanobu Habiro, Nobuaki Takane, and Mitsuo Yamada. Rewritable optical-disk fabrication with an optical recording material made of naphthalocyaning and polythiophene. Appl. Optics. 1995, 34:8201-8208
[60] 吴永忠．取代酞菁的光电性能研究[学位论文]．上海：华东理工大学，1996
[61] Achar B N,Fohlen G M and Parker. Heat-Resistant Poly(metal,Phtha-locyanine)imide Coplymers using Benzenetetracar-boxylic Dianhy-dride. J.A.J. Poly. Sci. Chem Ed 1985, 23 (3): 801-811
[62] Achar B N,Fohlen G M and Parker. Novel High-Temperature-Resis-tant Metal Phthalocyanine Imide Copolymers. J A. J. Poly. Sci. Chem Ed 1983, 21:3063-3072
[63] 刘宝殿，张耀刚：有机合成化学实验 邻苯二甲酰胺的合成30
[64] Joseph G.Young, William Onyebuagu; Synthesis and Characterri-
zation of Di-disubstituted phthalocyanine. J. Org. Chem. 1990, 55: 2155
[65] John Griffiths, Bizhan Roozpeikar; Synthesis and electronic absorption spectra of dicyano-deribative of 4-diethylaminoabenzene. J.C.S. Perkin I 1976, 42
[66] Han, Jiang hua; Bai, Bao lin; Zhao, Ming gen. Synthesis of schiff bases of digoethylene glyco bridged disalicylic aldehydes with anthranilic acid schiff base. Hua xue shi ji. 1995, 17 (6): 363-364
[67] 樊能延编著 有机合成事典。北京理工大学出版社
[68] Clifford C. Leznoff and Neil B. Mckeown Prepartion of Substituted Tetrabenzotriazaporphyrins and a Tetranaphthatriaza-porphyrin: A Route to Mono-meso-substituted Phthalocyanine Analogues J. Org. Chem. 1990,55:2186-2190
[69] Paul J. Brach, steven J. Grammatica, Oliver A Ossacha and Lester Weinberger. Improved Sythesis of metal-free phthalocyanine Webster, New York 14580
[70] Andreas Gouloumis, Shen-Gao Liu, Angela Sastre, Parificacion Vazquez, Luis Echegoyen and Torres Sythesis and Electrochemical Preperties of Pthalocyanine-Fullerene Hybrids. Chem. Eur. J 2000, 19:3600-3607
[71] 张先付、许慧君．取代锌酞菁的合成及光物理性质．高等学校化学学报 1994，6：917-919
[72] Achar B N, Fohlen G M and Parker. ?hthalocyanine Polymers Ⅳ. Novel Type of Thermally Stable Polyimides Derived From Metal Phthalocyanine Tetramines and Benzophenone Dianhydride. J. A. J. Poly. Sci. Chem Ed, 1982, 20:2773-2780
[73] Achar B N, Fohlen G M and Parker. Heat-Resistant Metal Phthalocyanine Imide Copolymers. J.A.J. Poly. Sci. Chem Ed, 1983, 21:1025-1032
[74] 赵剑波，赵福群，赵瑜，张复实等．空心酞菁光物理性质的取代基效应(英文) 物理化学学报 1996，12(6)：491-495
[75] Bredas, O.P. Chem. Mater. 1990, 2:110
[76] E. Elshereafy and M. A. Abd EL-Ghaffar; Eletrical and thermal studies on copper complexes of phthalocyanine and biphthalocyanine and their derivatives. Thermochimica Acta. 1991, 186:179-185
[77] 詹梦雄，郑标练，顾学民．厦门大学学报自然科学版．1986，25(2)：192-198
[78] K Burger. Coordination Chemistry, Experimental methods. London 1973, 8:315-334
[79] Lobayashi. N. M, Lever A. B.P.; Cation-or solvent-induced super-molecular phthalocyanine formation: crown ether substituted phthalocyanine. J. Am. Chem. Soc. 1987, 109:7433-7441