The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties |
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Authors: | Huriye Akdas-Kilig Jean-Pierre MalvalFabrice Morlet-Savary Anu SinghLoic Toupet Isabelle Ledoux-RakJoseph Zyss Hubert Le Bozec |
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Affiliation: | a SciencesChimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France b Institut de Sciences des Matériaux de Mulhouse, LRC CNRS 7228, Université de Haute Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France c Département de Photochimie Générale, Université de Haute-Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France d Laboratoire de Photonique Quantique et Moléculaire, UMR CNRS 8537, Institut d’Alembert, ENS Cachan, 61 avenue du Président Wilson, 94235 Cachan, France |
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Abstract: | Two new 4,4′-bis(donor)-6,6′-diphenyl- 2,2′-bipyridine ligands and their corresponding D2d (CuI, AgI, ZnII) octupolar metal complexes were synthesized, and their linear and nonlinear optical properties were investigated. A single crystal X-ray structure was also determined for the bis4,4′-bis(diethylaminostyryl)-6,6′-diphenyl-bipyridine]copper(I) complex, which revealed a distorded pseudo-tetrahedral geometry. Molecular second-order nonlinear optical properties were determined for the complexes using the Harmonic Light Scatterring technique at 1.91 μm. These metallo-chromophores display large first hyperpolarizabilities β1.91 in the range of 211-340 × 10−30 esu, which increase with the Lewis acidity of the metal ion. The two-photon absorption properties of the bipyridyl ligands and related complexes were determined using either the two-photon emission method for fluorescent compounds or the open aperture Z-scan technique for non emissive ones. The complexes display red-shifted two-photon absorption bands compared to their metal-ion free chromophores, as well as a large increase of the maximum two-photon absorption cross-sections. |
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Keywords: | Nonlinear optics Octupolar tetrahedral complexes Harmonic light scattering Two-photon emission fluorescence Z-scan Bipyridine |
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