Design, Synthesis, Morphology Controlled Self-assembled Organic Aggregation Based On Phthalocyaninato Complexes

As a novel functional materials, phthalocyanine compounds are easily modified, recently, phthalocyanines have been expected to be widely application in materials science, molecular electronics, molecular information storage, and nonlinear optics, etc; In the nature, chirality is one of the basic attributes, and molecular chiral and supramolecular chiral expression, transfer, storage and regulation are related with life phenomenon, With the development of science and technology, obtaining ordered supramolecular aggregates and nano-scale assembly, have attracted increasing attentions. We introduce chiral information to phthalocyanine molecules, then design molecules to adjust intermolecular forces, and in the molecular and supramolecular level the expression comes out, eventually we obtain what we want. And this is what we have been working for. This thesis mainly designed and synthesized new phthalocyanine compounds with special structure and properties. We have compounds assembled highly ordered aggregation through the molecular self-assembly, and through a series of characterization methods explore the molecular structure to find the effect to aggregate arrangement and relationship between aggregate morphology and properties. The contents mainly include:1. The Synthesis of Chiral Phthalocyanine, The Research of Supermolecular StructureChiral in regulation, control phthalocyanine molecular aggregate morphology plays a very important role, and the role of the coordination effect between Chiral induction effect and noncovalent interaction including π-π accumulation, metal coordination, especially the effect to structure dimension, the chiral and pitch of the size are our interests. In this chapter, we choose4,4’-dihydroxybiphenyl as a raw material, and (S)2-methylbutyl as chiral group sources, and we obtain metal free and zinc phthalocyanine on the basis of the above what we have synthesised, and then get the self-assembly aggregation through the solvent diffusion method, and finaly obtain self-assembly properties after a series of characterization methods. Research shows that Zn-O and chiral group induction effect should be responsible for the of aggregate morphology. The results provide a very useful information for our understanding the information of chirality on transmission, expression of supramolecular level, and the preparation, regulation of organic nano functional materials through the molecular design. In addition, good semi-conducting properties of the nanostructures fabricated from phthalocyanine derivatives1-3, respectively, were also revealed by Ⅰ-Ⅴ measurements.2. Research of Morphology Controlled Self-assembled Nanostructures of Thioether-PhthalocyaninesTo investigate the effect of sulfur-sulfur and metal-ligand coordination on the molecular structure and morphology of self-assembled nano-structures, metal free2,3,9,10,16,17,23,24-octakis-isopropylthiophthalocyanine H2Pc(β-SC3H7)8(1) and its copper CuPc(β-SC3H7)8(2) and lead PbPc((3-SC3H7)8(3) congeners have been synthesized and fabricated into organic nanostructures by a phase-transfer method. The self-assembling properties were investigated by electronic absorption and Fourier transform infrared (FT-IR) spectroscopy, transmission electronic microscopy (TEM), scanning electronic microscopy (SEM), X-ray diffraction (XRD) technique, and X-ray photoelectron spectroscopy (XPS). Experimental results reveal different molecular packing models in these aggregates, which in turn result in the self-assembled nanostructures with different morphology. These results imply the effects of the S-S,Cu-S,and Pb-S. In addition, good semi-conducting properties of the nanostructures fabricated from phthalocyanine derivatives1-3, respectively, were also revealed by I-V measurements.