Third-Order Optical Nonlinearities in Porphyrins with Extended π-Electron Systems

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Abstract
The third-order optical susceptibilities |χ1111 (3)(-3ω; ω, ω, ω)| for spin-coated films of free-base (H2) and MnCl-octaethyl[18]porphyrins, and N,N′,N′′,N′′′-tetramethyl-octaethyl[26]porphyrin-bistrifluoroacetate are determined by optical third-harmonic generation measurements at a wavelength of 1907 nm. The |χ(3)| values are 1.9×10-12, 2.6×10-12, and 1.0×10-11 esu for H2-[18]porphyrin, MnCl-[18]porphyrin, and [26]porphyrin, respectively. The enhancement of third-order nonlinear properties in macrocyclic compounds is discussed in terms of an extended π-electron system.