POLYMER EFFECTS ON REVERSIBLE FORMATION OF DIOXYGEN ADDUCT WITH SILVER(II) TETRAPHENYLPORPHYRIN MOIETIES

The anomalous behavior in the temperature dependence of ESR spectra ha s been discovered for the powder sample and LB film of ophenyl)-10,15, 20-triphenylporphyrinato]silver(II) (denoted by polyAgAATPP) under oxy gen atmosphere. The ESR intensity decreased with the decrease of tempe rature from room temperature to -150 degrees C. The IR and Raman spect roscopies at liquid nitrogen temperature revealed that the new IR-and Raman-active peaks appeared at 782 and 545 cm(-1) for the LB film of p olyAgAATPP under oxygen atmosphere, respectively. The peaks were assig ned to v(O-O) and v(Ag-O) in the dioxygen adduct of polyAgAATPP, respe ctively. The linkage between AgTPP moieties and dioxygen was likely to be of the bridging type. These phenomena were not observed for monome ric AgAATPP.