Study on preparation and some properties of new phtalocyanine complexes

合成了一些新的酞菁配合物，并对其性质进行了研究。（1）结构异构体Mpc中存在四种结构异构体，被四个取代基取代。然而，在pc环的α-位上引入大体积基团仅得到一种结构异构体，因此可以获得其镍（II）配合物的单晶。配合物的分子结构由X-射线晶体分析确定，显示螺旋型结构。（2）α-位树枝化的树枝状酞菁Znpc在二氯甲烷、苯等非极性溶剂中具有独特的吸收光谱。这可能是由于PC环的畸变通过锌（II）离子上的树枝化基元的氧原子的配位。（3）氧合催化剂研究了锰（Ⅱ）、铁（Ⅲ）、钴（Ⅱ）、镍（Ⅱ）、铜（Ⅱ）的pc配合物催化环己烯的氧合反应。该反应是促进由醛产生的过酸添加在溶液中和/或由羰基金属的pc络合物的中间体。（4）光催化剂用Znpcs作为光敏剂产生活性氧。它们在可见光照射下也能分解三氯苯酚。

Some new phthalocyanine (pc) complexes were prepared and the following properties were investigated.(1)Structural isomerFour structural isomers exist in Mpc substituted by four substituents. However, the introduction of bulky groups on the α-position of the pc ring only gives one structural isomer, and thus the single crystal of its nickel(II) complex could be obtained. The molecular structure of the complex was determined by an X-ray crystal analysis, showing a screw-type structure.(2)Dendrimer-phthalocyanineZnpc with dendrons on the α-position shows unique absorption spectra in non-polar solvents such as dichloromethane and benzene. This may result from the distortion of the pc ring by the coordination of the oxygen atom of dendron on the zinc(II) ion.(3)Oxygenation catalystOxygenation of cyclohexene catalyzed by pc complexes of manganese(II), iron(III), cobalt(II), nickel(II), and copper(II) was investigated. The reaction was promoted by peracid generated from aldehyde added in the solution and/or by an oxometal intermediate of the pc complex.(4)PhotocatalystAn active oxygen was generated using Znpcs as a photosenstizer. They also decomposed trichlorophenol in irradiation with visible light.