Study On Synthesis And Properties Of New Subsituted Phthalocyanines And Phthalocyanine Metal Complexes

Phthalocyanines have some special characteristics such as large stable π-conjugated system, special optical properties and chemical activities, which led to their use as dye and pigment, and potentials in the high tech appplications as functional materials, molecular-scale devices, and medicine because of their structure similar to porphyrin. Phthalocyanine and different metal elements in it can create a variety of metallic complexes. Different metal atoms can replace the two hydrogen atoms in the center of the planar molecule. The large ring of phthalocyanine is surrounded by16hydrogen atoms on four benzene rings. They could be replaced by many different atoms or groups to produce a vast number of different kinds of phthalocyanines and metallic phthalocyanines. In the thesis we mainly try to design and synthesize a series of new phthalocyanine compounds with special structure and properties based on the excellent clipping factor of phthalocyanine compounds. This dissertation mainly includes the following aspects:1. Synthesis of phthalonitrilesTwo new phthalonitrile compounds,3-(2-thiophenylmethoxyl)phthalonitrile and4-(2-thiophenylmethoxyl)phthalonitrile were designed and synthesized. Their structures were identified. The influences of the site of the substituent on the spectral properties of phtanlonitriles were investigated. It is found that different substitution position affects apparently the maximum absorbancy value in275～425nm range of the phthalonitriles.3-(2-Thiophenylmethoxyl)phthalonitrile showed stronger ultraviolet absorption and larger red-shift in the maximum absorption than 4-(2-thiophenylmethoxyl)phthalonitrile.2. Synthesis and characterization of new phthalocyanine compounds1,8(11),15(18),22(25)-Tetrakis(2-methoxythiophenyl)phthalocyanine and2,9(10),16(17),23(24)-tetrakis(2-methoxythiophenyl)phthalocyanine and their complexes with nickel, copper and zinc have been designed and synthesized. The new phthalocyanine compounds were charactered by IR, NMR and MOLDI-TOF-MS. The structure and spectroscopy were also tested and analysised.3. Spectral analysis of phthalocyninesPhthalocyanine compounds have been expected to be of wide applications in material science, owing to their unique optical and electronic properties, associated with the intriguing intramolecular π-π interactions. UV-Vis and fluorescence spectra of the new phthalocyanines have been measured to investigate their properties. It is found that introduction of methoxythiophenyl groups into phthalocyanines causes dramatic reduction of the Stokes shift. The fluorescence intensities of phthalocyanines with unmagnetic or closed shell electronic structures are stronger than those of phthalocyanines with a magnetic or opened shell structure.