The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties


Akdas-Kilig H. , Malval J., Morlet-Savary F., Singh A., Toupet L., Ledoux-Rak I., ...More

DYES AND PIGMENTS, vol.92, no.1, pp.681-688, 2012 (Journal Indexed in SCI) identifier

  • Publication Type: Article / Article
  • Volume: 92 Issue: 1
  • Publication Date: 2012
  • Doi Number: 10.1016/j.dyepig.2011.06.013
  • Title of Journal : DYES AND PIGMENTS
  • Page Numbers: pp.681-688
  • Keywords: Nonlinear optics, Octupolar tetrahedral complexes, Harmonic light scattering, Two-photon emission fluorescence, Z-scan, Bipyridine, 2-PHOTON ABSORPTION PROPERTIES, QUADRATIC HYPERPOLARIZABILITY, ORGANOMETALLIC COMPOUNDS, SENSITIVE MEASUREMENT, CONJUGATED MOLECULES, CRYSTAL-STRUCTURE, CROSS-SECTIONS, SINGLE-BEAM, COMPLEXES, CHROMOPHORES

Abstract

Two new 4,4'-bis(donor)-6,6'-diphenyl- 2,2'-bipyridine ligands and their corresponding D-2d (Cu-1, Ag-1, Zn-II) 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 bis[4,4'-bis(diethylaminostyryl)-6,6'-diphenyl-bipyridine]copper(1) 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 mu m. These metallo-chromophores display large first hyperpolarizabilities beta(1.91) in the range of 211-340 x 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. (C) 2011 Elsevier Ltd. All rights reserved.