Poly(arylene ether ketone)s with pendant porphyrins: Synthesis and investigation on optical limiting properties

This paper describes the synthesis and characterization of a novel series of poly(arylene ether ketone)s bearing porphyrin pendants, along with the demonstration of their nonlinear optical and optical limiting properties at 532 nm in both THF and films. The incorporation of pendant porphyrins was done through a modified esterification using a copoly(arylene ether ketone) with free carboxyl groups and mono-hydroxyphenyl porphyrins with different substituents and center metal. The introduction of porphyrin in the polymer was confirmed by IR, ¹H NMR, UV-vis, fluorescence spectroscopies, and WAXD. Investigation of thermal properties indicated that the poly(arylene ether ketone)s with porphyrin pendants possessed higher T_gs, and slightly lower decomposition temperatures than the starting copolymers. The results of optical limiting and Z-scan measurements demonstrated that the porphyrinated poly(arylene ether ketone)s exhibited strong optical limiting responses and nonlinear absorption properties with the nonlinear absorption coefficient β in the order of 10^-9 (m W^-1) magnitude. The effects of pendant porphyrin structure on the thermal, mechanical, linear and nonlinear optical properties of the poly(arylene ether ketone)s were investigated in detail.