具有Frétchet树枝结构的新型酞菁锌(Ⅱ)配合物:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(Ⅱ)的合成与表征  

Synthesis and Characterization of a Novel Frétchet Dendritic Phthalocyanine Zinc(II): Tetra-{3,5-di-[3,5-di-(4-carboxylic benzyloxy)benzyloxy]benzyloxy} Phthalocyanine Zinc(Ⅱ)

作　　者：贺丹丹[1] 张宏[1,2] 彭亦如[1] 马冬冬[1] 王瑜华[3] 杨洪钦[3] 陈婉玲[1] 张甜甜[1] He Dandan;Zhang Hong;Peng Yiru;Ma Dongdong;Wang Yuhua;Yang Hongqin;Chen Wanlin;Zhang Tiantian(College of Chemitry and Materials Science,Fujian Provincial Key Laboratory of Polymer Materials,Fujian Normal University,Fuzhou 350007;Key Lab of Optoelectronic Science and Technology for Medicine of Ministry of Education,Fujian Normal University,Fuzhou 350007;College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005)

机构地区：[1]福建师范大学化学与材料学院福建省高分子材料重点实验室,福州350007 [2]厦门大学化学化工学院,厦门361005 [3]福建师范大学医学光电科学与技术教育部重点实验室,福州350007

出　　处：《有机化学》2012年第7期1320-1326,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.60978071,20604007);福建省自然科学基金(Nos.2011J01029,2010J01322);卫生部科学研究基金(No.WKJ2008-2-61)资助项目

摘　　要：报道了一种新型Frétchet树枝配体取代酞菁锌(II)配合物:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(II)的合成与表征.首先将对氰基苄溴与3,5-二羟基苯甲醇通过Frétchet反应合成3,5-[二-(4-氰基苯甲氧基)]苯甲醇(1),1与四溴化碳和三苯基膦在四氢呋喃中反应合成3,5-二-(4-氰基苯甲氧基)苄溴(2),2与3,5-二羟基苯甲醇反应合成3,5-二-[3,5-二-(4-氰基苯甲氧基)苯甲氧基]苯甲醇(3),接着,3与4-硝基邻苯二甲腈合成"前驱物"四-{3,5-[二-(4-氰基苯甲氧基)]}苯甲氧基邻苯二甲腈(4),然后以1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)为催化剂,醋酸锌为模板剂,4通过缩聚反应合成氰基端基的Frétchet树枝配体取代酞菁锌四-{3,5-二-[3,5-二-(4-氰基苯甲氧基)苯甲氧基]-苯甲氧基}锌酞菁配合物5,最后,5的氰基端基在NaOH溶液中水解为相应的以羧基端基Frétchet树枝配体取代酞菁锌:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(II)(6).采用元素分析,IR,1H NMR,ESI-MS和MALDI-TOF-MS表征所有化合物的结构,通过UV/Vis,稳态和瞬态荧光光谱法研究了5和6的光物理性质.5和6是一类性能较好的树枝状酞菁光敏剂.A novel Fr6tchet structural dendritic substituted photosensitizer,tetra-{3,5-di-[3,5-di-(4-carboxylic benzyloxy)-benzyloxy]benzyloxy}phthalocyanine zinc(II)(6),was synthesized by the following steps.Firstly,3,5-di-(4-cyanobenzyloxy)benzyl alcohol(1)was obtained by reaction of 3,5-di-hydroxybenzyl alcohol with p-cyanobenzylbromide.Then,3,5-di-(4-cyanobenzyloxy)benzyl bromide(2)was synthesized by the reaction of I with carbon tetrabromide in the presence of triphenylphosphine and tetrahydrofuran.Following,2 reacted with 3,5-di-hydroxybenzyl alcohol to afford 3,5-di-[3,5-di-(4-cyanobenzyloxy)benzyloxy]benzyl alcohol(3).The fragment 4-{3,5-di-[3,5-di-(4-cyanobenzyloxy)benzyloxy]}phthalonitrile(4)was obtained by reaction of 3 with 4-nitrophthalonitrile.Tetra-{3,5-di-[3,5-di-(4-cyanobenzyloxy)benzyloxy]benzyloxy}phthalocyanine zinc(II)(5)was obtained by condensation of 4 with acetate zinc and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU)in n-pentanol.The tetra-{3,5-di-[3,5-di-(4-carboxylic benzyloxy)benzyloxy]benzyloxy}phthalocyanine zinc(II)(6)was obtained by hydrolyzed 5 in NaOH.The structures of above compounds were characterized by a combination of methods including elemental analysis,1H NMR,IR,ESI-MS and MALDI-TOF-MS.The photophysical properties of 5 and 6 were studied by UVfVis,steady state and transient fluorescence spectrometry.The compound 6 is a kind of good performance of dendritic photosensitizer.

关 键 词：四-{3 5-二-[3 5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(Ⅱ) 合成 表征 Frétchet树枝 

分 类 号：O627.23[理学—有机化学]