Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers

Benjamin J. Coe, James A. Harris, Lathe A. Jones, Bruce S. Brunschwig, Kai Song, Koen Clays, Javier Garín, Jesús Orduna, Simon J. Coles, Michael B. Hursthouse

    Research output: Contribution to journalArticlepeer-review

    Abstract

    In this article, we describe a series of new complex salts in which electron-donating cis-{RuII(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 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. These experiments reveal that these dipolar pseudo-C2v chromophores exhibit two substantial components of the β tensor, βzzz and βzyy, 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. © 2005 American Chemical Society.
    Original languageEnglish
    Pages (from-to)4845-4859
    Number of pages14
    JournalJournal of the American Chemical Society
    Volume127
    Issue number13
    DOIs
    Publication statusPublished - 6 Apr 2005

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