Issue 41, 2023

Mechanism of optical limiting in metalloporphyrins under visible continuous radiation

Abstract

Here, we present an experimental investigation on the nonlinear optical (NLO) and optical limiting properties of metalloporphyrin compounds (Cu-1-OH, Zn-1-OH, Cu-1-E and Zn-1-E) using spatial self-phase modulation (SSPM) method in the visible range. It is found that all of the samples show a large self-defocusing effect at 532 nm, which is attributed to the thermal nonlinear optical effects with negative nonlinear refractive index coefficient n2 due to the relatively high absorption at 532 nm. In contrast, at 780 nm where absorption is weak for both Zn- and Cu-porphyrins, Zn-porphyrins still exhibit visible self-defocusing while Cu-porphyrins do not show any nonlinear diffraction pattern. Such a phenomenon can be explained by the Kerr effect of Cu-porphyrins at 780 nm. As the thermal nonlinear optical effects (of negative n2) at 780 nm are reduced due to the low absorption, the Kerr effect with positive n2 becomes comparable and the overall nonlinearity is reduced. The Kerr effect of Cu-porphyrins is stronger than that of Zn-porphyrins because of the enhanced π-electron delocalization effect as Cu(II) has a variable number of valence electrons and incompletely filled d atomic orbitals. Finally, the optical limiting performance of Zn-porphyrins is demonstrated as a representative and its dependence on sample position is examined. This work not only enriches the understanding of the physical mechanism of optical limiting in porphyrin materials, but also provides a significant reference to improve the third-order NLO coefficient by adjusting the structure of compounds.

Graphical abstract: Mechanism of optical limiting in metalloporphyrins under visible continuous radiation

Article information

Article type
Paper
Submitted
29 Jun 2023
Accepted
22 Sep 2023
First published
12 Oct 2023

Phys. Chem. Chem. Phys., 2023,25, 28213-28219

Mechanism of optical limiting in metalloporphyrins under visible continuous radiation

Q. Zhang, B. Lu, S. Liu, X. Lü and X. Cheng, Phys. Chem. Chem. Phys., 2023, 25, 28213 DOI: 10.1039/D3CP03055E

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