Synthesis and characteristics of poly(3,4-azopyridylene)(PAP),conductivity and oxygen-binding affinity of its complex with meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinatocobalt(II)(COP)were studied.PAP was p...Synthesis and characteristics of poly(3,4-azopyridylene)(PAP),conductivity and oxygen-binding affinity of its complex with meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinatocobalt(II)(COP)were studied.PAP was prepared by oxidative polymerization of 3,4-diaminopyridine(DAP)in DMF solution using CuCl/pyridine as the catalyst.IR and NMR results showed that the peak of amido group in DAP was converted to the azo group in PAP and a π conjugated polymer was synthesized.The average molecular weight of PAP was determined to be 5.0×10~3.The PAP-CoP complex was prepared by complexing the pyridyl group of PAP with the fifth coordination site of CoP in DMF solution.In comparison with the CoP complex with a non-π conjugated polymer,the PAP-CoP complex shows good electroconductivity of 5.8×10^(-6) S cm^(-1).The PAP-CoP complex displays a reversible change in the UV-Visible absorption spectrum from the deoxy form to the oxy or oxygen-binding one with an isosbestic point,in response to the partial oxygen pressure of the atmosphere.The oxygen- response behavior was monitored at the absorbance ascribed to the oxy form at 548 nm to give the oxygen-binding affinity. The oxygen-binding equilibrium curves of PAP-CoP complex obey a Langmuir isotherm.DMF has great effects on the oxygen-binding properties of the PAP-CoP complex.The oxygen-binding affinity of PAP-CoP complex in the solid state is higher than that in DMF solution.With decreasing temperature,the oxygen-binding affinity of the PAP-CoP complex increases.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.50373035)Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘Synthesis and characteristics of poly(3,4-azopyridylene)(PAP),conductivity and oxygen-binding affinity of its complex with meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinatocobalt(II)(COP)were studied.PAP was prepared by oxidative polymerization of 3,4-diaminopyridine(DAP)in DMF solution using CuCl/pyridine as the catalyst.IR and NMR results showed that the peak of amido group in DAP was converted to the azo group in PAP and a π conjugated polymer was synthesized.The average molecular weight of PAP was determined to be 5.0×10~3.The PAP-CoP complex was prepared by complexing the pyridyl group of PAP with the fifth coordination site of CoP in DMF solution.In comparison with the CoP complex with a non-π conjugated polymer,the PAP-CoP complex shows good electroconductivity of 5.8×10^(-6) S cm^(-1).The PAP-CoP complex displays a reversible change in the UV-Visible absorption spectrum from the deoxy form to the oxy or oxygen-binding one with an isosbestic point,in response to the partial oxygen pressure of the atmosphere.The oxygen- response behavior was monitored at the absorbance ascribed to the oxy form at 548 nm to give the oxygen-binding affinity. The oxygen-binding equilibrium curves of PAP-CoP complex obey a Langmuir isotherm.DMF has great effects on the oxygen-binding properties of the PAP-CoP complex.The oxygen-binding affinity of PAP-CoP complex in the solid state is higher than that in DMF solution.With decreasing temperature,the oxygen-binding affinity of the PAP-CoP complex increases.
