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Title: Two-dimensional, pyrazine-based nonlinear optical chromophores with ruthenium(II) ammine electron donors
Authors: Coe, Benjamin J ×
Fielden, John
Foxon, Simon P
Asselberghs, Inge
Clays, Koen
Brunschwig, Bruce S #
Issue Date: Nov-2010
Publisher: American Chemical Society
Series Title: Inorganic Chemistry vol:49 issue:22 pages:10718-26
Abstract: Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru(II)(NH(3))(5)}(2+) or trans-{Ru(II)(NH(3))(4)(py)}(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru(II) centers from one to two, but remain at constant energy. One or two Ru(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant "off-diagonal" β(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β(0). Both the HRS and the Stark-derived β(0) values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru(II) ammine complexes reported previously.
URI: 
ISSN: 0020-1669
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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