Design, Synthesis, Characterization And Self-assembly Properties Of Chiarl Phthalocycanine And Porphyrinato/Phthalocycaninato Double-decker Complexes

Owing to the unique optical, electrical, and properties, porphyrins, phthalocyanines, as well as sandwich type rare complexes, as a novel functional material, have been expected to be widely potential application in materials science. Recently, it is significantly interested in ordered supramolecular aggregates 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 designing molecular to controlle and optimize inter-molecular interaction still remains a great challenge for chemists and material scientists. In order to extensively investigate the effect of the central mental ions on molecular structure and supramolecular aggregation morphology, in this thesis a series of phthalocyanine and sandwich mixed type rare complexes complexes derivatives are selected. And a series of characterization methods were performed to examine their aggregate structures, morphologes and nanostructures. Our research work has been focused on the following respects:1、Self-assembled Nanostructures of Optically Active Phthalocyanine Derivatives. Effect of Central Metal Ion on the Morphology, Dimension, and Handedness:To investigate the effect of metal-ligand coordination on the molecular structure and morphology of self-assembled nano-structures, Four optically active {(2,3,9,10,16,17,23,24-octa[(S)-2-methylbutoxy]} phthalocyanine derivatives with different central metal ion, namely (S)-H2Pc(β-OC5H11)8(1),(S)-ZnPc(P-OC5H11)8(2),(S)-CuPc(β-OC5H11)8(3), and (S)-NiPc(β-OC5H11)8(4) have been synthesized and their self-assembly behaviors systematically investigated by electronic absorption and circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) technique. The results clearly revealed the effect of central metal ion on the distance and relative orientation of neighboring phthalocyanine chromophores and in turn the supramolecular chirality, morphology, dimension, and handedness of the self-assembled nanostructures. The present result not only represents a unique phenomenon in the self-assembly of phthalocyanine compounds but more importantly denotes the transcription and amplification of molecular chirality to supramolecular helicity with different helical bias during the self-assembly processes without changing the chiral handles attached to the phthalocyanine chromophore. 2、Crystal Structure and Self-assembly Property of Sandwich-type Mixed (Phthalocyaninato)(porphyrinato) Rare Earth Double-decker Complexes:we describe the crystal structure and self-assembly property of two mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes M(Pc)(TPP)[H2Pc=phthalocyanine; H2TPP=meso-tetra(phenyl)porphyrin](M=Eu, Lu)(1,2). Comparative investigation over the single crystal and nano-structure X-ray diffraction analysis results of the two double-decker complexes reveal the same molecular packing mode and intermolecular distance for both compounds. Comparative studies between the europium and lutetium analogues in the two mixed ring double-deckers clearly reveal the effect of molecular structure on the dimension of self-assembled nano-structures.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.