摘要
结合本研究组的工作, 简要总结了迄今文献上所发表的取代酞菁金属配合物的结构研究结果, 包括四取代、八取代、十六取代、内环取代以及不等同取代等。
A review on the crystal structures of ring-substituted plithalocyanines (Pc or Pcs) reported in literature so far in connection with those solved by our research group is given in this paper. For the convenience of description, the 30 crystal structures are divided according to their substitution types into tetra-, octa-, hexadeca-, non-equivalent and inner-ring-substituted configurations. In the tetra-substituted Pcs, the planar configuration of Pc ring system is maintained, and the Pc rings are pushed mutually by the introduced substituents, leading to a series of structural caves to allow the insertion of solvent molecules, as found in compound 3. In the octa-substituted Pcs, space hindrance may exist between the substituents of neighboring iso-indolenes, and it can be relaxed either by changing the orientation of substituents or by the saddle deformation of the Pc rings. Both two possible structural variants are found in different compounds. I For hexadeca-substituted Pcs, four compounds listed in Table 3 are reported. It is interesting to note that compound 22 has a special catalytic activity which can couple phosphanes with acetone to produce ylides and water at ambient condition, as shown in the following formula PPh3 + CH3C(=O)CH3 + 1/2O(2) --> Ph3P=CHC(=O)CH3 Concerning the non-equivalent substituted Pc, only one compound with formula 1,4-(C4H9O)(2)-2,3(Py)2-8,11,15,18,22,25-(C6H13)(6)PCZn has been reported so far. In this structure, three isoindolenes are substituted by two hexyl groups, and the other one by two pyridyl and two butoxy groups, so that it is a ten substituted compound in fact. Not only can the 16 ring H atoms be substituted by other groups or atoms, but also the carbon atoms at the inner ring can be combined with suitable groups or atoms. The compounds with formulas {(CH3O)(2)Pc}NiCH3OH and {(CH3CH2O)(2)}Ni belong to this type, in which the connection of inner ring carbons with substituents leads to the saddle distortion of the ring systems. In addition, the so-called 'bicyclic' type compound can also be included in this respect. At the end of this paper a prospect has been made that the development of this area is going to open a new branch of supramolecules based on the phthalocyanine planar skeleton.
基金
福建省自然科学基金资助项目(E0310007)
