Title: Pentacyanoiron(II) as an electron donor group for nonlinear optics: Medium-responsive properties and comparisons with related pentaammineruthenium(II) complexes
Authors: Coe, Benjamin J ×
Harries, Josephine L
Helliwell, Madeleine
Jones, Lathe A
Asselberghs, Inge
Clays, Koen
Brunschwig, Bruce S
Harris, James A
Garin, Javier
Orduna, Jesus #
Issue Date: Sep-2006
Publisher: Amer chemical soc
Series Title: Journal of the American Chemical Society vol:128 issue:37 pages:12192-12204
Abstract: In this article, we describe a series of complex salts in which electron-rich {Fe-II(CN)(5)}(3-) centers are coordinated to pyridyl ligands with electron-accepting N-methyl/aryl-pyridinium substituents. These compounds have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d -> pi* metal-to-ligand charge-transfer (MLCT) bands. The relatively large static first hyperpolarizabilities, beta(0), increase markedly on moving from aqueous to methanol solutions, accompanied by large red-shifts in the MLCT transitions. Acidification of aqueous solutions allows reversible switching of the linear and NLO properties, as shown via both HRS and Stark experiments. Time-dependent density functional theory and finite field calculations using a polarizable continuum model yield relatively good agreement with the experimental results and confirm the large decrease in beta(0) on protonation. The Stark-derived beta(0) values are generally larger for related {Ru-II(NH3)(5)}(2+) complexes than for their {Fe-II(CN) (5)} (3-) analogues, consistent with the HRS data in water. However, the HRS data in methanol show that the stronger solvatochromism of the Fe-II complexes causes their NLO responses to surpass those of their Ru-II counterparts upon changing the solvent medium.
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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