Design, Synthesis, Self-assembly And Nonlinear Optical Properties Of Chiarl Phthalocycanine Complexes

As the novel functional materials, phthalocyanine has a large potential application in molecular materials, nonlinear optical materials, liquid crystal materials and catalyst. In recent years, ordered supramolecular aggregates and nano-scale assembly of phthalocyanine compounds have become a hot topic in the field of functional materials. The preparation, signal amplification, storage, memory processes and properties of chiral compounds are interested to scientists. We attempt to find the way to introduce the chiral signal into the phthalocyanine ring to make it successfully expressed in the supramolecular level through rationally design the molecular structure by adjusting intermolecular forces. How to obtain the organic nanostructures with controllable self-assembly morphology is also a major challenge. This thesis designed and synthesized two phthalocyanine derivatives with different substituents and their corresponding metal complexes. We discussed the effects of substituents at different positions in the phthalocyanine ring, indicated the influence of central metal ion on the expression of chiral signal and studied the morphology of self-assembly phthalocyanine aggregates. These efforts are conducive to design the molecular structure and product chiral nano-materials with controllable morphology. Our work is focused on the following respects:1%Effect of substituents position to phthalocyanine properties, Influence of the central metal to morphology of aggregatesAs a class macrocycle, phthalocyanine could combine with a variety of metallic elements to form a coordination bond. Thereby change the morphology, dimension, and handedness of phthalocyanine. In this chapter, three phthalocyanine derivatives (S)-H2Pc(a-OC5H11)4(1)(S)-ZnPc(a-OC5H11)4(2) and (S)-H2Pc(P-OC5H11)4(3)have been designed and synthesized. The CD spectra showed CD signal in the Q absorption region of phthalocyanine chromophore of compounds1and2. However, no CD signal was observed in the whole absorption region of phthalocyanine chromophore of compound3. These results indicated the effectively influence of the position of the chiral substituents on the chiral transfer and expression at molecular level. Further investigation about the self-assembly behavior of compounds1and2revealed the metal free phthalocyanine1self-assembled into the nano-cube. Its zinc congener (S)-ZnPc(a-OC5H11)4(2) self-assembled into helical nano-belts, implying the effect of metal-coordination on the morphology and handedness of the self-assembled nanostructures. This will help us to rational design of phthalocyanine molecules, then develop applications in chiral catalysts and nano-molecular devices, molecular materials, etc.2、Self-assembled Nanostructures of Optically Active Phthalocyanine Derivatives. Research on the Nonlinear Optical PropertiesPreparation of chirality and morphology controllable phthalocyanine nano-structured materials is an important issue. Two phthalocyanine derivatives with eight peripheral chiral diethyleneglycol mono-(S)-2-methylbutyl ether moieties on the β-position of the phthalocyanine ring were prepared. The self-assembly behavior of metal free phthalocyanine1and its copper congener2have been comparatively investigated by electronic absorption and circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) technique, and X-ray photoelectron spectroscopy (XPS). The metal free phthalocyanine self-assembles into the right-handed screw-like aggregates, while, phthalocyaninato copper compound2self-assembled into left-handed fibrous aggregates. These results indicated the effect of metal-coordination bond on the morphology and handedness of the self-assembled nanostructures. Further, excellent nonlinear optical (NLO) properties of both compounds were also revealed by a Z-scan experiment, which expand their applications in nonlinear optics. This will provide a lot of help for us to rational design and preparation of some chiral functional nano-materials and nonlinear optical materials...