In this work, we have prepared a series of A4 ZnII porphyrins, carrying in the β-pyrrolic-position one or two π-delocalized ethynylphenyl moieties with a -NO2 acceptor or a -NMe2 donor pendant, and measured their second-order NLO response in CHCl3 solution at 1907 nm via the electric-field-induced second harmonic generation (EFISH) technique. For some of these compounds, we have recorded an unexpected sign and/or absolute value of μβ1907. Since their sterically hindered A4 structure should ensure the lack of significant aggregation processes in solution, we explain such anomalous EFISH results by invoking a non-negligible contribution of the electronic cubic term γ(-2ω; ω, ω, 0) to γEFISH, as supported by a qualitative evaluation of the third-order response through the measure of the cubic hyperpolarizability (γTHG) and by computational evidence.

Electric-Field-Induced Second Harmonic Generation Nonlinear Optic Response of A4 β-Pyrrolic-Substituted ZnII Porphyrins: When Cubic Contributions Cannot Be Neglected / G. Di Carlo, M. Pizzotti, S. Righetto, A. Forni, F. Tessore. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - (2020 May 15). [Epub ahead of print] [10.1021/acs.inorgchem.0c00451]

Electric-Field-Induced Second Harmonic Generation Nonlinear Optic Response of A4 β-Pyrrolic-Substituted ZnII Porphyrins: When Cubic Contributions Cannot Be Neglected

G. Di Carlo
Primo
;
M. Pizzotti
Secondo
;
S. Righetto;F. Tessore
2020

Abstract

In this work, we have prepared a series of A4 ZnII porphyrins, carrying in the β-pyrrolic-position one or two π-delocalized ethynylphenyl moieties with a -NO2 acceptor or a -NMe2 donor pendant, and measured their second-order NLO response in CHCl3 solution at 1907 nm via the electric-field-induced second harmonic generation (EFISH) technique. For some of these compounds, we have recorded an unexpected sign and/or absolute value of μβ1907. Since their sterically hindered A4 structure should ensure the lack of significant aggregation processes in solution, we explain such anomalous EFISH results by invoking a non-negligible contribution of the electronic cubic term γ(-2ω; ω, ω, 0) to γEFISH, as supported by a qualitative evaluation of the third-order response through the measure of the cubic hyperpolarizability (γTHG) and by computational evidence.
Settore CHIM/03 - Chimica Generale e Inorganica
15-mag-2020
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/735152
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