Diarylethene-based Photochromic Tetrazaporphyrin And Phthalocyaninato Derivatives: Synthesis, Properties And Their Self-assemblies

Due to the potential application in optical recording,information storage,pigment, organic photohromic compounds has attract more and more attentions.Among these kinds of photochromic compound,diarylethene,especially bisthienylethene has been the focus of attention because of their outstanding thermal stability and fatigue resistance.These years,a lot of efforts have been devoted to synthesizing these kinds of photochromic compounds,which not only contains the synthesis of new molecule materials with better performace,but also contains the modification of the molecules with the functional group.The main aim of this dissertation is to explore the new and effective method for the synthesis of tetrazaporphyrin or phthalocyaninato with BTE substituent,which will not only improve the photochromic performance of the compounds,but also facilitate the self-assemblies of the molecules based on intra-molecularÏ€-Ï€interactions.The main points of thedissertations are summarized as follows:1,Synthesis of TAP-BTE zinc complex with photochromic property and its application in non-destructive readoutA photochromic 1,2-bisthienylethenes(BTEs) substituted tetraazaporphyrinato(TAP) zinc complex, 2,3,7,8,12,13,17,18-octakis(2',4',5'-trimethyl-3'-thienyl)tetraazaporphyrizine zinc,was synthesized by "one-pot" reaction,and was characterized by spectroscopic methods as well as the elemental analysis.The changes in the electronic absorption spectrum and ¹H-NMR indicate that this BTE-TAP hybrid underwent reversible photocyclization and cycloreversion by irradiation with 365 and 730 nm light in CHCl₃ solution,respectively. However,the reversible photocyclization only occurs on the BTE group in the opposite position.The macromolecules of tetrazaporphin restricted the symmetrical structure of BTE group,which greatly improved the photochromic performance of the compounds. Comparisons between the experimental and computational IR spectra clarified the significant difference of the open- and closed-ring isomers,which indicate that this diarylethene derivative can be used in non-destructive readout by IR light at 1705 cm^-1. The absorption peak at 1441 and 1489cm-1can also be used in the identification of the photocyclization process.Decrease of the molecule symmetry or increase the molecular dipole moment will change the IR vibration intenstity,which will greatly facilitate the nor-destructive readout process.The photo-luminescence properties of the compounds are also investigated,which clearly shows that the spectrum of the compound greatly changed before and after the photocycliztion process.The possibilities of using the PL spectrum as the non-destructive readout method are also carefully discussed.2.Tetrazaporphyrin substituted with crown ether and diarylethen group:synthesis, characterizations and its self-assembliesA series of novel tetraazaporphyrinato(TAP) copper compounds substituted with different number of 15-crown-5 voids and photochromic 1,2-bisthienylethenes(BTEs) 1-5 were synthesized by "one-pot" reaction,and were characterized by spectroscopic methods as well as the elemental analysis.The effects of BTE and 15-crown-5 substituents number and molecular symmetry on the electronic absorption spectra, infra-red(IR) spectra,photochromic performance are carefully investigated.All the BTE-TAP hybrids have presented photocyclization and cycloreversion with different quantum yield by irradiation with 365 and 700 nm light in CHCI3 solution,respectively. Considering the existence of 15-crown-5 ether group in the molecules,the interfacial self-assemble behavior of the compound are also investigate,which clearly demonstrate that the steric hindrance derived from the BTE(s) substituents embarrasses the cofacial dimerization of the compounds,and only linear dimers formed as a result.The number of 15-crown-5 ether group and the open/close state of the ring will greatly affect the morphologies of the aggregates.3,A template method for the synthesis of crown ether substituted tetrazaporphyrin zinc hollow spheresA plate-like tetraazaporphyrinato(TAP) zinc compounds substituted with different number of 15-crown-5 voids and photochromic 1,2-bisthienylethenes(BTEs) 1-5 were synthesized by "one-pot" reaction.The compound show amphilic property due to the hydrophilic property of 15-crown-5 group and hydrophobic property of BTE group. This compound has been prove to form uniformly-sized multilarnellar hollow nanospheres with a mean diameter of 200 nm under the template construction of potassium ions.Scanning Electron Microscopy(SEM),transmission electron microscopy(TEM),Electron Dispersion Spectrum(EDS),X-ray Diffraction(XRD) and electron absorption spectrum are employed to characterize the structure and component of the hollow spheres.Based on the experimental facts,potassium ion template formation mechanism of the hollow spheres is proposed.In these nanoparticles,the addition of K⁺ restricted the chirality transfer from the peripheral,which finally lead to the loss of helicity of the compound.This kind of controllable chiral material will have potential application in optical electric materials and sensors.4,Novel sandwiched complex with BTE substituted tetrazaporphyrin and phthalocyanines:synthesis,characterizations and its properties.A conventional route which is usually used in the synthesis of phthalocyaninato are employed in the synthesis of tetrazaporphyrin derivatives,which finally lead to the first sandwiched rare earth complex Eu₂[TAP(C₇H₉S)₈][Pc(15C5)₄]₂.The ¹H-NMR,IR, Mass,elemental analysis and electron absorption spectrum are employed to characterize the compound.Our study shows that this compound show excellent photochromic performance.It can tune the scope of conjugation by the ring open or ring close reaction, which is applicable due to is novelty and facility.