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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 new type of Frétchet dendrimer ligand was substituted for the zinc phthalocyanine (II) complex: tetrakis- {3,5-bis- [3,5-bis- (4-carboxybenzyloxy) benzyloxy] Benzyloxy} phthalocyanine (II) was synthesized by Friedel-Crafts reaction of 3, 5 - [bis- (4-cyanobenzoyl) (2) is reacted with carbon tetrabromide and triphenylphosphine in tetrahydrofuran to synthesize 3,5-bis- (4-cyanobenzyloxy) benzyl bromide (2), 2 and 3,5-di- [3,5-bis- (4-cyanobenzyloxy) benzyloxy] benzyl alcohol (3) is synthesized by the reaction of 3,5-dihydroxybenzyl alcohol with Nitro-phthalonitrile Synthesis of “precursor” tetrakis- [3,5-bis- (4-cyanobenzyloxy)]} benzyloxyphthalonitrile (4) Using the zinc acetate as templating agent with 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) as catalyst and the Frétchet dendrimer ligand with cyano end group synthesized by polycondensation instead of phthalocyanine Zinc tetrakis- {3,5-bis- [3,5-bis- (4-cyanobenzyloxy) benzyloxy] -benzyloxy} zinc phthalocyanine complex 5, finally, The base end is hydrolyzed in NaOH solution to the corresponding zinc phthalocyanine substituted with the carboxy terminal Frétchet branch ligand: tetrakis- {3,5-di- (6). Using elemental analysis, IR, 1H NMR, ESI-MS and The structures of all the compounds were characterized by MALDI-TOF-MS. The photophysical properties of 5 and 6 were studied by UV / Vis, steady-state and transient fluorescence spectroscopy .5 and 6 are a class of dendrimeric phthalocyanine photosensitizers .