New supramolecular compounds based on porphyrin and polyoxometalate: synthesis, characterization and nonlinear optical and optical limiting properties

Abstract

Three new supramolecular compounds [H₂TPP]_1.5[SW₁₁VO₄₀]·5CH₃CN·4H₂O 1, [H₂TPP]₂[SW₁₀V₂O₄₀]·4CH₃CN·3H₂O 2, and [H₂TPP][SW₁₂O₄₀]·4H₂O 3 composed of [H₂TPP]²⁺ cation and vanadium substituted Keggin-type polyoxometalate (POM) anion [SW_12−nV_nO₄₀]⁽²⁺ⁿ⁾⁻ (n = 0–2) were prepared and characterized. The third-order nonlinear optical (NLO) and optical limiting (OL) properties of resulting hybrids were studied by using an Nd:YAG laser at 532 nm with a pulse duration of τ = 7 ns. The results demonstrate that all of these supramolecular compounds have significant nonlinear reverse saturated absorption, self-defocusing behavior, and good OL performance, especially for compound 1, which has a second hyperpolarizability γ value of 7.05 × 10⁻²⁹ (esu) and exhibits a comparable OL performance with the most well-known OL materials such as In(Pc*)Cl indicating that they are potentially excellent NLO materials. Remarkably, it was also observed that the degree of vanadium substitution in POM anions corresponding to different onset of reduction potential influences the NLO and OL properties of the resulting compounds: third-order NLO and OL properties of compound 2 are inferior to those of compound 1, and are better than those of compound 3. Both their second hyperpolarizability γ values and the OL performance were observed to be inversely proportional to the HOMO–LUMO gaps of the resulting compounds. The excited charge transfer from porphyrin to POM anions in the supramolecular compounds when exposed to laser irradiation is thought to play key role in the enhancement of NLO and OL response.