Morphology Controlled Self-assembled Nanostructures Of Porphyrinato/Phthalocyaninato Complexes

With the development of science and technology, the investigation and application of new functional materials have been the main task for production and life. Owing to the unique optical, electrical, and properties, porphyrins, phthalocyanines, as well as sandwich type rare complexes, as a novel functional materials, have been expected to be widely potential application in materials science. Recently, it is significantly interested in ordered supramolecular aggregate and nanoscale assembly fields. However, it must be pointed out that self-assembly of functional molecules into a prerequisite nanostructure with desirable dimension and morphology via controlling and optimizing inter-molecular interaction still remains a great challenge for chemists and material scientists. In order to extensively investigate supramolecular aggregation behaviors and supramolecular assembly methodology of porphyrinato and/or phthalocyninato complexes, in this thesis a series of porphyrin and/or phthalocyanine derivatives are selected, and some modern measuring techniques were performed to examine their aggregate structures, morphologes and nanostructures. In this dissertation, our research work has been focused on the following respects:1. Dimension Controlled Self-assembled Nano-structures of Sandwich-type Mixed (Phthalocyaninato)(porphyrinato) Rare Earth Double-decker Complexes. Pure Effect of Molecular DimensionTwo series of sandwich-type mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes, M(Pc)(TPP) [M= Eu (1), Lu (2)] and MⅢ(Pc)[D(NHC8H17)2PP] [M= Eu (3), Lu (4)] [Pc= dianion of phthalocyanine; TPP= dianion of 5,10,15,20-tetra(phenyl)porphyrin; D(NHC8H17)2PP= dianion of 5,10-di(phenyl)-15,20-di(4-octylamino-phenyl)porphyrin] have been designed, synthesized, and their self-assembled nano-structures have been systematically investigated. Comparative investigation over the single crystal and nano-structure X-ray diffraction analysis results of both series of the double-decker complexes reveal the same molecular packing mode and intermolecular distance for both compounds. This renders it possible to disclose the pure effect of molecular structure, actually the molecular dimension in the direction perpendicular to the tetrapyrrole ring on the dimension and morphology of nano-structures due to the almost same intermolecular interaction associated with the same molecular packing mode, same intermolecular distance, and similar molecular weight.2. Morphology Controlled Self-assembled Nanostructures ofThioether-Phthalocyanines. Effect of Metal-ligand CoordinationTo investigate the effect of metal-ligand coordination on the molecular structure and morphology of self-assembled nano-structures, metal free 2,3,9,10,16,17,23,24-octakis-isopropylthiophthalocyanine H2Pc(P-SC3H7)8 (1) and its derivatized complexs CuPc(β-SC3H7)g (2) and PbPc(β-SC3H7)g (3) 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), and X-ray diffraction (XRD) techniques. Experimental results reveal different molecular packing models in these aggregates, which in turn result in the self-assembled nanostructures with different morphology from nanobelts for 1, nanoribbons for 2, and to nanobelts with cluster formation for 3. Inter-molecularπ-πand sulfur-sulfur interactions between metal free phthalocyanine molecule 1 lead to the formation of nanobelts; For phthalocyaninato lead complex 2, metal-ligand coordination bonding tunes the morphology into nanoribbons; Nanobelts with cluster formation formed from the phthalocyanine derivative 3 based on van der Waals interaction and metal-ligand coordination between neighboring Pb-connected pseudo-double-decker building blocks.