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Length-Dependent Convergence and Saturation Behavior of Electrochemical, Linear Optical, Quadratic Nonlinear Optical, and Cubic Nonlinear Optical Properties of Dipolar Alkynylruthenium Complexes with Oligo(phenyleneethynylene) Bridges
Journal of the American Chemical Society (2009)
  • Bandar Babgi, Australian National University
  • Luca Rigamonti, Australian National University
  • Marie P. Cifuentes, Australian National University
  • T. Christopher Corkery, Australian National University
  • Michael D. Randles, Australian National University
  • Torsten Schwich, Australian National University
  • Simon Petrie, Australian National University
  • Robert Stranger, Australian National University
  • Ayele Teshome
  • Inge Asselberghs
  • Koen Clays
  • Marek Samoc
  • Mark G. Humphrey, Australian National University
Abstract
The syntheses of trans-[Ru{4,4′-C≡CC6H2[2,5-(OEt)2]C≡CC6H4NO2}Cl(dppm)2] (19), trans-[Ru{4,4′,4′′-C≡CC6H4C≡CC6H2[2,5-(OEt)2]C≡CC6H4NO2}Cl(dppm)2] (20), trans-[Ru{4,4′,4′′,4′′′-C≡CC6H4C≡CC6H2[2,5-(OEt)2]C≡CC6H2[2,5-(OEt)2]C≡CC6H4NO2}Cl(dppe)2] (21), trans-[Ru{4,4′,4′′,4′′′-C≡CC6H4C≡CC6H2[2,5-(OEt)2]C≡CC6H2[2,5-(OEt)2]C≡CC6H4NO2}Cl(dppm)2] (22), trans-[Ru{4,4′,4′′,4′′′-C≡CC6H4C≡CC6H4C≡CC6H2[2,5-(OEt)2]C≡CC6H4NO2}Cl(dppm)2] (23), and trans-[Ru{4,4′,4′′,4′′′,4′′′′-C≡CC6H4C≡CC6H4C≡CC6H2[2,5-(OEt)2]C≡CC6H2[2,5-(OEt)2]C≡CC6H4NO2}Cl(dppm)2] (24) are reported, together with those of precursor alkynes, complexes with the donor−π-bridge−acceptor formulation that affords efficient quadratic and cubic NLO compounds; the identity of 19 was confirmed by a structural study. The electrochemical properties of 19−24 and related complexes with shorter π-bridge ligands were assessed by cyclic voltammetry, and the linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties were assayed by UV−vis−NIR spectroscopy, hyper-Rayleigh scattering studies at 1064 and 1300 nm, and broad spectral range femtosecond Z-scan studies, respectively. The RuII/III oxidation potentials and wavelengths of the optical absorption maxima decrease on π-bridge lengthening, until the tri(phenyleneethynylene) complex is reached, further chain lengthening leaving these parameters invariant; theoretical studies employing time-dependent density functional theory have shed light on this behavior. The quadratic nonlinearity β1064 and two-photon absorption cross-section reach maximal values at this same π-bridge length, a similar saturation behavior that may reflect a common importance of ruthenium-to-alkynyl ligand charge transfer in electronic and optical behavior in these molecules.
Disciplines
Publication Date
2009
Citation Information
Bandar Babgi, Luca Rigamonti, Marie P. Cifuentes, T. Christopher Corkery, et al.. "Length-Dependent Convergence and Saturation Behavior of Electrochemical, Linear Optical, Quadratic Nonlinear Optical, and Cubic Nonlinear Optical Properties of Dipolar Alkynylruthenium Complexes with Oligo(phenyleneethynylene) Bridges" Journal of the American Chemical Society Vol. 131 Iss. 29 (2009)
Available at: http://works.bepress.com/chriscorkery/8/