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Published September 28, 2005 | Supplemental Material
Journal Article Open

Three-Dimensional Nonlinear Optical Chromophores Based on Metal-to-Ligand Charge-Transfer from Ruthenium(II) or Iron(II) Centers

Abstract

In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' ''-quaterpyridinium ligands. These complexes contain either Ru^(II) or Fe^(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses β have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D_3 chromophores exhibit two substantial components of the β tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts.

Additional Information

© 2005 American Chemical Society. Received June 13, 2005. Publication Date (Web): August 30, 2005. We thank the EPSRC for support (Grant GR/M93864), and also the Fund for Scientific Research-Flanders (FWO-V, G.0297.04), the University of Leuven (GOA/2000/3), the Belgian Government (IUAP P5/3), MCyT-FEDER (BQU2002-00219), and Gobierno de Aragon-Fondo Social Europeo (E39).

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