Synthesis And Properties Of Functional Phthalocyanines Derivatives

Phthalocyanines(Pcs)and Subphthalocyanines(SPcs)are both conjugated macrocycle aromatic molecules and show intense absorption and fluorescence in the visible region making them possible to be excellent chromophores.There has been considerable interest in phthalocyanines(Pcs)because of their diverse potential applications in a wide range of different fields such as nonlinear optics,thin films,organic solar cells,and especially photodynamic therapy(PDT).Due to the 14π-electron aromatic system of SPc,it shows intense absorption(550-600 nm)and fluorescence in the visible region and makes it possible to be an excellent light-harvesting unit.Due to conical structure and easily axial ligand exchange,multi-functional subphthalocyanines not only apply to organic photodetectors,molecular cages and probes.Based on the above excellent properties of Pcs and SPcs,we designed and synthesized a Pcs derivative of photodynamic therapy properties,and photochromic materials based on SPcs.The results of dissertation are summarized as follows:1.A novel phosphorus triazatetrabenzcorrole has been synthesized by using the corresponding free base Pc as the precursor in a ring-contraction reaction.In DMSO,the PⅤTBC complex has a high singlet oxygen quantum yield(ΦΔ=0.63)and a moderate fluorescence quantum yield(ΦF=0.20),making it potentially useful for theranostics.When PVTBC PLGA nanoparticles were introduced into U87MG cells they displayed high PDT efficiency when excited at 660 nm in the biological window for tissue penetration.2.We have synthesized two novel azobenzene-SPc compounds 16 and 17.Numerous reversible isomerization of 16 is found that cis→ trans is induced within the Q band region of subphthalocynaine.Significantly,a decrease in the fluorescence intensity of trans→cis and the recovery of cis→trans are observed,which verifies that the fluorescence emission of 16 could be modulated by the isomerization state of the azobenzene moiety.The the isomerization of 17 is similar to 16.The difference is that the absorption of azobenzene moiety of 17 is at 385 nm,and the change of isomerization is smaller than 16.3.A novel subphthalocyanine-dithienylethene complex 25 has been synthesized by using the 1,2-bis[2-methyl-5-(4-hydroxyphenyl)-3-thienyl]cyclopentene and subphthalocyanine as the precursors in an axial exchange reaction.The photoisomerization process of SubPc-DTE dyad is investigated by UV-visible spectra by irradiating open form solution at λ=312 nm and closed form solution at λ=570 nm.Significantly,the decrease and recovery in the fluorescence intensity of the SubPc moiety were also observed during photoisomerization of SubPc-DTE dyad,which verified that the fluorescence emission of SubPc-DTE dyad could be modulated by the isomerization state of the DTE moiety.