Study On Fabrication And Application Of Novel Phthalocyanines And Self-assembly Nanostructures

Recently, phthalocyanines and their derivatives have received considerable attention due to their excellent physical and chemical properties and they have shown potential application in optoelectronic devices. Phthalocyanines with special structures, such as unsymmetrical phthalocyanines and optically active phthalocyanines, have stronger advantages in the application than the ordinary phthalocyanines due to their unique characteristics. For example, amphiphilic unsymmetrical phthalocyanines could be good films. And unsymmetrical phthalocyanines with push and pull groups have good electrical properties. However, the difficulty in synthesis greatly restricted their applications. In this dissertation, a series of novel unsymmetrical metal phthalocyanines have been synthesized by modifying the classical synthetic method. The reaction mechanism and the electrochemical properties have been studied. Other optically active phthalocyanines have also been synthesized and their transformation temperature was studied. Afterward the phthalocyanines nanofibers have been obtained in large scale by a novel self-assembly method. The mechanism of the formation of the phthalocyanine fibers has been discussed and the size of the fibers could be finely tuned under different conditions. Finallyγ-radiation dosimeter has been obtained by hydro soluble metal phthalocyanines. Following are the summarization of the main work:(1)Synthesis and electrochemical properties of a series of novel unsymmetrical metal phthalocyaninesBy modifying the condition of the classical synthetic method, a series of novel unsymmetrical metal phthalocyanines, (2-isopropylphenoxy)-tri-(5-methyl-2-isopropylphenoxy) nickel/copper phthalocyanine and (4-isopropylphenoxy)-tri-(4-tert-butylphenoxy) phthalocyanines, were synthesized. The method has good selectivity with fewer by-products and was easy to be purified. The method was suitable for different phthalocyanines with similar structure and various metals. The phthalocyanines were characterized by MS, FT-IR, HRMS and UV-Vis.The UV-Vis-Nir spectra were affectrd by the central metals. With the ability of push-electron of the substitutents increasing,λmax in Q band of the prepared MPcs shift to red region slightly. The nir spectra of the metal phthalocyanines were discussed. Novel broad peaks of the unsymmetrical phthalocyanines were found, which were different with the symmetrical phthalocyanines. It was considered that the peaks were caused by the electron transition interlayer. The unsymmetrical phthalocyanines could be used as nir detectors. We studied the cyclic votammograms electrochemistry of these metal phthalocyanines. The results suggest that the redox reactions of these metal phthalocyanines are occurred in the Pc ring. They were quasi-reversible process. The proposed electrochemical reaction mechanism was discussed.(2) Synthesis and transformation temperature of novel optically active phthalocyanines.Novel optically active phthalocyanines, tetra-β-(S)-2-octanyloxy phthalocyanines with copper and nickel, have been synthesized by enzyme-catalysis resolution and characterized. The novel phthaclocyanines could dissolve in various solutions except methanol. The optically active phthalocyanines favor to form face-to-face H-type aggregates with left helix in the films prepared by deposition. The study by differential scanning calorimetry showed that no obvious phase transition temperatures exsist and they are sticky solid among a wide temperature scope from -50-300℃. This may be the positional isomers that impact the purity of them.(3) Preparation of one-dimensional nanofibers and the properties of optoelectronic devices of the metal phthalocyanines.A simple, cost-effective and large-scale method to synthesize metal phthalocyanines nanofibers was developed. The metal phthalocyanines nanofibers were fabricated by mixed solvent self-assembly route for the first time. The formation of the nanofibers was established by the XRD and UV-Vis spectra, which could be understood by three interactions of molecules: theπ-πinteraction of the phthalocyanines rings; theπ-πinteraction between the benzene rings of the substituent of the neighbour phthalocyanines; M-O coordination bond between the neighbour phthalocyanines.The sizes of the fibers can be finely tuned under different reaction temperature. The length of the fibers changed from several decade micrometers to several hundreds nanometers and the width changed from several decade nanometers to several micrometers. It's because the diffusion velocity of the solution was affected by the temperature.Nanofibers of CuPc1 (tetraphenoxyl-substituted CuPc) were fabricated into nanodevice of photoswitcher, in which the nanofibers were installed on an interdigital electrode. The device was capable to switch on/off reversibly and fast by turning the 808 nm infrared light source on/off. The sensitivity was high, the response was fast and the recovery time was short. EFISPS demonstrate that the CuPc1 nanowires have photovoltaic response and are a kind of p-type semiconductor due to the orderly arrangement of phthalocyanines inside the sample. (4) Hydrosoluble metal phthalocyanines asγ-radiation dosimeter.A novelγ-radiation dosimeter by sulfonic Fe/Co phthalocyanines was obtained. The sulfonic metal phthalocyanines dosimeter exhibited a good liner response toγ-radiation of dose less 600 Gy. The CoTSPc had higher Decolorization degree than FeTSPc. The sulfonic metal phthalocyanines could be used as aγ-radiation dosimeter.