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Excited‐State Dynamics of a Two‐Photon‐Activatable Ruthenium Prodrug
Authors:Dr. Simon E. Greenough  Michael D. Horbury  Dr. Nichola A. Smith  Prof. Dr. Peter J. Sadler  Prof. Martin J. Paterson  Dr. Vasilios G. Stavros
Affiliation:1. Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, UK;2. Department of Chemistry, University of Sheffield, Sheffield, UK;3. Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, UK
Abstract:We present a new approach to investigate how the photodynamics of an octahedral ruthenium(II) complex activated through two‐photon absorption (TPA) differ from the equivalent complex activated through one‐photon absorption (OPA). We photoactivated a RuII polypyridyl complex containing bioactive monodentate ligands in the photodynamic therapy window (620–1000 nm) by using TPA and used transient UV/Vis absorption spectroscopy to elucidate its reaction pathways. Density functional calculations allowed us to identify the nature of the initially populated states and kinetic analysis recovers a photoactivation lifetime of approximately 100 ps. The dynamics displayed following TPA or OPA are identical, showing that TPA prodrug design may use knowledge gathered from the more numerous and easily conducted OPA studies.
Keywords:density functional calculations  ligand substitution  ruthenium  time-resolved spectroscopy  two-photon absorption
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