Syntheses and spectroscopic and quadratic nonlinear optical properties of extended dipolar complexes with ruthenium(II) ammine electron donor and N-methylpyridinium acceptor groups |
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Authors: | Coe Benjamin J Jones Lathe A Harris James A Brunschwig Bruce S Asselberghs Inge Clays Koen Persoons André Garín Javier Orduna Jesús |
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Institution: | Department of Chemistry, University of Manchester, Oxford Road, Manchester, United Kingdom M13 9PL. b.coe@man.ac.uk |
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Abstract: | In this paper, we describe the extremely unusual optical properties of Ru(II)-based electron donor-acceptor (D-A) polyene and some closely related chromophores. For three different polyene series, the intense, visible d-->pi* metal-to-ligand charge-transfer bands unexpectedly blue-shift as the number of E-ethylene units (n) increases from 1 to 3, and the static first hyperpolarizabilities beta(0) determined via hyper-Rayleigh scattering and Stark spectroscopy maximize at n = 2, in marked contrast to other known D-A polyenes in which beta(0) increases steadily with n. Time-dependent density-functional theory and finite field calculations verify these empirical trends, which arise from the orbital structures of the complexes. This study illustrates that transition metal-based nonlinear optical chromophores can show very different behavior when compared with their more thoroughly studied purely organic counterparts. |
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