Preparation Of Macrocyclic Functional Molecule Self-assembled Structure,and Its Performance Research

Macrocyclic functional molecules and its self-assembled aggregates have recently a growing attraction with promising performance because of their successful application in optical and electronic devices.These devices include organic solar cells(OSC),organic thin film transistors(OTFT),and organic light-emitting diodes(OLEDs).In recent years,Phthalocyanines are studied as well-defined molecular in high technological area such as,chemical sensors,semiconductors,electrochromic display devices,liquid crystals,solar cells,photovoltaics,various catalytic processes,and photosensitizers for photodynamic cancer therapy.Because of the extended p-type,phthalocyanine compounds exhibit a tendency in solution to form the dimer and higher oligomeric species therefore,many phthalocyanines have been restricted in application areas owing to their lower solubility in common organic solvents due to aggregation.Therefore,our main synthetic aims is that soluble phthalocyanines in common organic solvents with bearing suitable functional groups.Our research work has been mainly focused on the following two respects:First,through a simple solution self-assembly strategy,two different morphological nanostructures of 2,3,9,10,16,17,23,24-octakis(phenoxy)phthalocyaninato manganese(?)complex(Mn Cl[Pc(OPh)8]),with good uniformity and monodispersity,are successfully fabricated.The self-assembly behavior of the Mn Cl[Pc(OPh)8]compound in non-coordinating and coordinating mixed solvents(chloroform/n-hexane and chloroform/methanol)have been comparatively investigated by electronic absorption,Fourier transform infrared spectroscopy(FT-IR),scanning electronic microscopy(SEM)and X-ray diffraction(XRD)techniques.Depending mainly on the intermolecular?-?interaction between the phthalocyanine rings,this phthalocyaninato manganese complex self-assemble into rod-like nanostructures with H-type aggregation in chloroform/n-hexane.In contrast,the Mn-O coordination interactions between the hydroxyl oxygen in solvated methanol molecule and manganese center of neighbouring Mn Cl[Pc(OPh)8]molecule,lead to the formation of spherical nanostructures with J-type aggregation in chloroform/methanol.Thus,these results clearly reveal the solvent coordination effect on intermolecular interaction and the morphology of the self-assembled Mn Cl[Pc(OPh)8]nanostructures.In addition,the nonlinear optical properties of Mn Cl[Pc(OPh)8]aggregates indicate that reverse saturation absorption for nanorods and saturation absorption for nanospheres due to difference in the size of self-assembled nanostructures..Secondly,the novel 2,3,9,10,16,17,23,24-octakis[4-(trifluoromethyl)phenoxy]phthalocyaninato copper complex(Cu Pc(OPh CF3)8])derivatives(Pc:Phthalocyanine)has been synthesized for the first time and their structures characterized by using FT-IR,MALDI-TOF/MS and UV-vis spectral.Through the introducing of electron-withdrawing4-(trifluoromethyl)phenoxy substituents into the periphery of phthalocyanine ring,Cu Pc(OPh CF3)8 complex exhibited n-type semiconductor property due to the change of LUMO energy level.On the other hand,the self-assembled film morphology of this copper phthalocyanine complexes were investigated by scanning electron microscope(SEM)and atomic force microscope(AFM)as complementary technic based on novel Cu Pc(OPh CF3)8]was fabricated with Si O2/Si as the gate dielectric material.We have also investigated electrical characterization of the OTFT of the new Cu Pc(OPh CF3)8]semiconductor material.While source and drain contacts of the device were coated with Au,the organic field effect property of Cu Pc(OPh CF3)8]self-assembled film exhibited saturation at the order of?_FET of 0.03±0.002 cm² V^-1 s^-1(V_ds,-40 V)and 0.004±0.0003cm² V^-1 s^-1(V_ds,80V),I_on/I_off and V_ds of this device are 2×10² and 80 V,using a simple epitaxial solution method,respectively.In the end,we report the self-assembly process of micro-scaled 5,10,15,20-tetra(4-phenyl)porphyrinato zinc(Zn TPP)coordination polymer particles(CPPs)via the self-assembly method controlled by surfactant.The fluorescence of different 3D micro-Zn TPP CPPs display different aggregate morphology indicating the different molecular aggregation in the self-assembled octahedral and linear of Zn TPP.Based on the results of electrical conductivity test,the Zn TPP self-assembled aggregates with one-dimensional(1D)nanostructure present good electroconductivity,about 1.78×10^-7 S·m^-1This result also indicats that the improved potential of the Zn TPPself-assembled nanostructures in the field of functional nanodevice materials.