Design, Synthesis, Organic Aggregation And Spectroscopic Properties Of Chiral Phthalocycanine And Rare Earth Sandwich Complexes

Chirality which is closely related with the nature of life is one of the basic attributes of nature. Chiral molecules are most basic unit in the life system. Owing to the unique optical, electrical, and properties, associated with the intriguing intramoleculaπ-πinteractions, porphyrins, phthalocyanines, as well as sandwich type rare complexs as a novel functional materials, have been expected to be widely potential application in materials science, such as molecular electronics, molecular information storage, and nonlinear optics, etc. Recently, to obtain ordered supramolecular aggregates and nano-scale assembly, besides the expression, transmission, storage and regulation of molecular/ supramolecular's chirality, have attracted increasing attentions.It must be pointed out that self-assembly of functional molecules into a prerequisite nanostructure with desirable dimension and morphology via controlling inter-molecular interaction and the introduced chirality informations still remains a great challenge for scientists. In order to investigate supramolecular aggregation behaviors, supramolecular assembly methodology of chiral phthalocyninato complexs, the role of coordination bond in tuning the aggregates's morphology and the expression of chiral information at molecular / supramolecular level, in this thesis several chiral phthalocyanine derivatives are designed and synthesized. Our research work has been focused on the following respects:1. Synthsis and Novel Helical Nano-structures of Optically Active Metal PhthalocyanineNovel optically active metal phthalocyanine (1) decorated with four butoxy chains linked to the phthalocyanine ring was designed and prepared. Helical Nano-structures Self-Assembled from Optically Active Phthalocyanine Derivatives Bearing Four Optically Active butoxy:Effect of Metal-ligand Coordination on the Morphology, Dimension, and Helical Pitch of Self-Assembled Nano-structures. Compound 1 was prepared from the tetramerization of corresponding phthalonitriles, S-3-(2'-methel butoxy) phthalonititrile, in the absence and presence of Zn (OAc)2-2H2O template, respectively, promoted by organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Their self-assembly behavior has been comparatively investigated by electronic absorption and circular dichroism (CD) spectroscopy, transmission electron microscope(TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) technique, and X-ray photoelectron spectroscopy (XPS). The metal phthalocyanine self-assembles into highly ordered fibrous nano-structures with right-handed helicity through the hierarchical manner via one-dimensional helices with chirality determined by the optically active butoxy side chains, revealing the effect of metal-ligand coordination bonding interaction on the morphology, dimension, handedness, and the helical pitch of self-assembled nano-structures.2. Mixed (Phthalocyaninato)(Porphyrinato) Rare Earth Double-Decker Complexes:Synthsis and spectroscopic studiesWe are motivated to design and prepare new chiral sandwich-type phthaiocyaninato and porphyrinato rare earth complexs with a view to creating novel applications in material science and catalysis. The strategy towards chiral sandwich-type tetraphyrrole rare earth complexes involves utilization of 1,8,15, 22-tetrakis (octyloxy)-substituted phthalcoyanine ligand. In the present chapter, we describe the synthesis and spectroscopic studies of mixed (phthalocyaninato) (porphyrinato) rare earth double-decker complexes [EuPc*(TClPP)] (compound1)] and [EuHPc*(TClPP)](compound2)][(Pc*=Pc(α-D-2-octyloxy)4). These two compounds were characterized by 1HNMR, MS and various spectroscopic methods including IR, UV-vis and CD. Their UV-vis and CD spectra are different. Both compounds display CD signal in the Soret absorption region of mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes, indicating effective chiral information transfer from the chiral peripheral substituents to compound chromophore at the molecular level. And the intensity of CD signal is different between the compound1 and compound2.