Experimental analysis of excited state dynamics in Anderson-type POM@porphyrin hybrids in relevance to third-order nonlinear optical properties

Abstract

This work accounts for the active contribution of life time decay in the field of nonlinear optics, especially for an energetic donor acceptor couple (porphyrin and polyoxometalate (POM)). Currently, two POM free porphyrins (Di-Tris-N@Por and Di-Tris@Por) and their two hybrids with POM (Di-Tris-NPor@Di-AndPOM-1 and Di-TrisPor@Di-AndPOM-2) have been studied keenly in nanosecond time span and resulted lifetimes ([Formula: see text]1 and [Formula: see text]2) have been compared with nonlinear optical parameters. The results demonstrated that Di-Tris-NPor@Di-AndPOM-1 exhibited better third-order nonlinear optical susceptibility [Formula: see text]3, second hyperpolarizability [Formula: see text] and nonlinear absorption [Formula: see text] and Di-TrisPor@Di-AndPOM-2 than Di-TrisPor@Di-AndPOM-2. This superiority of nonlinear optical parameters was supported by lifetime decay studies and electrochemical studies. It is revealed that more relaxation time in excited states lower will be the NLO response. The lifetime decay ([Formula: see text]1) value of Di-Tris-NPor@Di-AndPOM-1 is 3.86ns which is higher than Di-TrisPor@Di-AndPOM-2 possessing lifetime decay ([Formula: see text]1) value of 2.45ns. Moreover, lower energy of charge separated state (-0.88 eV) of Di-Tris-NPor@Di-AndPOM-1 indicates the facile electron transfer in Di-Tris-NPor@Di-AndPOM-1 than Di-TrisPor@Di-AndPOM-2 which experienced more energy of charge separated state. Rapid intersystem crossing is also responsible for the electron transfer from porphyrin moiety to POM moiety.