title: Excited-State Dynamics of a Two-Photon-Activatable Ruthenium Prodrug.
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 Ru(II) 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.
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK.|Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.
authors.forename: Simon E
authors.initials: SE
authors.lastname: Greenough
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK.
authors.forename: Michael D
authors.initials: MD
authors.lastname: Horbury
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK.
authors.forename: Nichola A
authors.initials: NA
authors.lastname: Smith
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK.
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Sadler
authors.affiliation: Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
authors.forename: Martin J
authors.initials: MJ
authors.lastname: Paterson
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK. v.stavros@warwick.ac.uk.
authors.forename: Vasilios G
authors.initials: VG
authors.lastname: Stavros
mesh_terms: D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D017785:Photons; D011355:Prodrugs / Q000737:chemistry*; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D011355:Prodrugs; D012428:Ruthenium
keywords: density functional calculations; ligand substitution; ruthenium; time-resolved spectroscopy; two-photon absorption