一种新型的平面共轭的酞菁卟啉二联体的合成及光谱研究(英文)

Fusing Phthalocyanine and Porphyrin together:Unprecedented Co-planar Ring-Fused Diazaphthalocyaninato-porphyrin Dimers

5,10,15,20-四(4-氯苯基)-2′,3′-二氰基[2,3-β]卟啉和4,5-二(丁烷氧基)邻二氰基苯在锂存在的条件下在正戊醇中回流四聚,然后用醋酸处理得到了一种新型的平面共轭酞菁二联体H4{[(DAPc(OC4H9)6][TClPP]}(1)(其中DAPc(OC4H9)6是2,3,9,10,16,17-六(丁烷氧基)-22,25-二氮杂酞菁的二价阴离子,TClPP是5,10,15,20-四(4-氯苯基)卟啉的二价阴离子)。这种二联体和Zn(OAc)2.2H2O在DMF和甲苯混合溶剂中反应得到双金属配合物Zn2{[(DAPc(OC4H9)6][(TClPP)]}(2)。质谱和核磁共振光谱等一系列的表征方法证明了这种双核的混杂四吡咯结构。电子吸收光谱和磁圆二色谱证明了酞菁发色团和卟啉发色团之间存在有效的分子内电子相互作用。这一结论进一步得到了理论计算的支持。

An unprecedented ring-fused co-planar diazaphthalocyaninato-porphyrin dimer H4{[（DAPc（OC4H9）6] [TClPP]}（where DAPc（OC4H9）6 is the dianion of 2,3,9,10,16,17-hexa（butyloxy）-22,25-diazaphthalocyanine,and TClPP is the dianion of 5,10,15,20-tetra（4-chloro）porphyrin）（1） was synthesized by mixed cyclic tetramerization of 5,10,15,20-tetrakis（4-chlorophenyl）-2′,3′-dicyanopyrazino[2,3-β] porphyrin with 4,5-di（butyloxy）phthalonitrile in the presence of lithium in refluxing n-pentanol followed by treatment with acetic acid.Reaction of the metal free dimer with Zn（OAc）2.2H2O in DMF and toluene led to the isolation of a bimetallic zinc（Ⅱ） complex Zn2{[（DAPc（OC4H9）6] [（TClPP）]}（2）.The binuclear and mixed tetrapyrrole ring nature of the structure was clearly demonstrated by a series of characterization methods including mass spectrometry and NMR spectroscopy.The Q band region of the electronic absorption and magnetic dichroism（MCD） spectra provide evidence for significant intramolecular interaction between the phthalocyanine and porphyrin chromophores.Theoretical calculations provide further support for this.