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)

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 Frétchet 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 1 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-(4Chinese Journal of Organic Chemistry NOTE Chin.J.Org.Chem.2012,32,1320～1326 2012 Chinese Chemical Society & SIOC,CAS http://sioc-journal.cn/ 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 UV/Vis,steady state and transient fluorescence spectrometry.The compound 6 is a kind of good performance of dendritic photosensitizer.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---

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