Title: Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers
Authors: Coe, BJ ×
Harris, JA
Jones, LA
Brunschwig, BS
Song, Kai
Clays, Koen
Garin, J
Orduna, J
Coles, SJ
Hursthouse, MB #
Issue Date: Apr-2005
Publisher: Amer chemical soc
Series Title: Journal of the American Chemical Society vol:127 issue:13 pages:4845-4859
Abstract: In this article, we describe a series of new complex salts in which electron-donating -cis{Ru-parallel to{NH3)(4)}(2+) centers are connected to two electron-accepting N-methyl/aryl-pyridinium groups. These V-shaped complexes contain either monodentate 4,4'-bipyridyl-derived ligands or related chelates based on 2,2':4,4":4',4"'-quaterpyridyl and have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses Pi have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d -> pi* metal-to-ligand charge-transfer bands. These experiments reveal that these dipolar pseudo-C-2v chromophores exhibit two substantial components of the beta tensor; beta(zzz) and beta(zyy), with the difference between them being most marked for the nonchelated systems. Time-dependent density-functional theory and finite field calculations serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts.
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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