Synthesis Of New-sandwich Type Rare Earth Phthalocyanine Complexes And Electrochemical Sensing Performance Research

As a novel functional materials with outstanding electrical,optical,and magnetic properties,associated with the macrocyclic conjugation system,phthalocyanine and phthalocyanine derivatives based on metal coordination,have been studied and widely used in the field of material science.The sandwich phthalocyanine with high three-dimensional conjugate has a strong?-?interaction between the intramolecular conjugate macrocycles,which makes the molecule have a suitable first oxidation and first reduction potential difference?HOMO-LUMO energy level difference?,wider electrochemical window,higher conductivity,thus showing more unique electrochemical performance and good catalytic activity.This provides a huge development space for sandwich phthalocyanine in the field of electrochemical sensing.In this paper,two novel sandwich phthalocyanine complexes containing phthalocyanine dimer were designed and synthesized,a series of characterizations of internal structures,surface morphology and electrochemical sensing properties of the compounds were carried out,and electrochemical sensing devices were obtained with higher sensitivity.This paper mainly includes the following several parts:?1?A binuclear phthalocyanine dimer-containing europium double-decker complex[{Pc?SC₂H₅?₈}Eu{BiPc?SC₂H₅?₁₂}Eu{Pc?SC₂H₅?₈}]has been designed,synthesized,and characterized.The complex further expands the?-conjugated system and possesses good solubility.Using the solution-processing QLS method a facile approach has developed for preparing the electrochemical sensor of novel[{Pc?SC₂H₅?₈}Eu{BiPc?SC₂H₅?₁₂}Eu{Pc?SC₂H₅?₈}]based on the ITO electrodes at the air/water interface.Electrochemitry sensing suggested the sensitive detection of APAP and AA with the good sensitivities of 254 and 85.6 mA?M^-1 cm^-2 and low detection limits of 1.3 and 3.7?mol/L,respectively.More importantly,a simultaneous determination of APAP and AA at a coexisting system of APAP and AA is also achieved with the still good sensitivities of 110 and 186.5 mA?M^-1 cm^-2,and low detection limits of 1.0 and 4.9?mol/L for APAP and AA respectively.?2?A novel sandwich complex containing phthalocyanine dimer[Pc?SC₂H₅?₈]₂Eu₂[BiPc?SC₂H₅?₁₂]Eu₂[Pc?SC₂H₅?₈]₂ has been synthesized.The framework structure of the dimer phthalocyanine has been expanded and conjugated vertically and horizontally to form a five-layer compound containing dimer phthalocyanine.A simple and low-cost QLS method has been used to prepare the compound into self-assembled films and build electrochemical sensing electrodes on the surface of ITO,which have been achieved high sensitivity detection of dopamine and uric acid.It is worth noting that this sandwich phthalocyanine with novel structure has been applied in the study of electrochemical sensing with the good sensitivities of 254 and 85.6 mA?M^-1 cm^-2 and low detection limits of 13.5 and 1.64?mol/L for APAP and AA respectively for the first time.