Study On Structures And Spectra Of Alkoxy Substituted Phthalocyanines And Their Analogue

Twelve alkoxy substituted phthalocyanines have been synthesized by DBU method or alkoxy lithium method in this part. They are listed as follows: (CH3CH2O)8MPc (M=2H,Cu,Ni,Co), (RO)8ZnPc [R=CH3CH2-, CH3(CH2)3-, CH3(CH2)4-, CH3(CH2)7-], [CH3(CH2)4O]8CuPc, [CH3(CH2)7O]8Co)Pc , (RO)4ZnPc (R=iso-Pentyl, 2,2,4-trimethyl-3-Pentyl). Four structures of these compounds{(CH3CH2O)8MPc (M=Cu,Ni), [CH3(CH2)4O]8CuPc, [CH3(CH2)7O]8CoPc} have been determined by X-ray single-crystal analyses. Some of these compounds have been characterized by IR spectra, UV/Vis spectra, solid-state reflectance spectra, fluorescence spectra and 1H NMR spectra. The crystal structures showed that the conformation of skeleton of some substituted Pc deviate from planarity, compared with that of non-substituted Pc, and it is not only caused by the steric effect of the neighboring substituents, but also by the aggregation between the molecules.In the study of UV/Vis spectra, it is found that some of alkoxy substituted phthalocyaninatozinc showed a new band (named as X bands) at the longer wavelength side of the Q band. It is assigned to the band of protonation at the azomethine bridges according to the monomeric and aggregate UV/Vis spectra, fluorescence spectra, 1H NMR spectra and the protonation spectra of six phthalocyaninatozinc compounds.Key Words: phthalocyanines;crystal structure;spectroscopic characterization...