Title: Combining Very Large Quadratic and Cubic Nonlinear Optical Responses in Extended, Tris-Chelate Metallochromophores with Six pi-Conjugated Pyridinium Substituents
Authors: Coe, Benjamin J ×
Fielden, John
Foxon, Simon P
Brunschwig, Bruce S
Asselberghs, Inge
Clays, Koen
Samoc, Anna
Samoc, Marek #
Issue Date: Mar-2010
Publisher: Amer chemical soc
Series Title: Journal of the american chemical society vol:132 issue:10 pages:3496-3513
Abstract: We describe a series of nine new complex salts in which electron-rich Ru-II or Fe-II centers are connected via pi-conjugated bridges to six electron-accepting N-methyl-/N-arylpyridinium groups. This work builds upon our previous preliminary studies (Coe, B. J. J. Am. Chem. Soc. 2005, 127, 13399-13410; J. Phys. Chem. A 2007, 111, 472-478), with the aims of achieving greatly enhanced NLO properties and also combining large quadratic and cubic effects in potentially redox-switchable molecules. Characterization has involved various techniques, including electronic absorption spectroscopy and cyclic voltammetry. The complexes display intense, visible d -> pi* metal-to-ligand charge-transfer (MLCT) bands, and their pi ->pi* intraligand charge-transfer (ILCT) absorptions in the near-UV region show molar extinction coefficients as high as ca. 3.5 x 10(5) M-1 cm(-1). Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 and 1064 nm and also via Stark (electroabsorption) spectroscopic studies. The directly and indirectly derived beta values are very large, with the Stark-based static first hyperpolarizabilities beta(0) reaching as high as ca. 10(-27) esu, and generally increase on extending the pi-conjugation and enhancing the electron-accepting strength of the ligands. Cubic NLO properties have also been measured by using the Z-scan technique, revealing relatively high two-photon absorption cross sections of up to 2500 GM at 750 nm.
ISSN: 0002-7863
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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