title: Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission.
abstract: We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 (2-) dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 (2-) ⋅ thymine and PtCl6 (2-) ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 (2-) ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl6 (2-) ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 (2-) ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a "dynamic tag" which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to allow autodetachment.
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
authors.forename: Ananya
authors.initials: A
authors.lastname: Sen
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
authors.forename: Edward M
authors.initials: EM
authors.lastname: Matthews
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352, USA.
authors.forename: Gao-Lei
authors.initials: GL
authors.lastname: Hou
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352, USA.
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
authors.forename: Caroline E H
authors.initials: CE
authors.lastname: Dessent
mesh_terms: D002945:Cisplatin / Q000031:analogs & derivatives* / Q000737:chemistry; D004247:DNA / Q000737:chemistry*; D004583:Electrons; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D012313:RNA / Q000737:chemistry*
chemical_list: D012313:RNA; D004247:DNA; D002945:Cisplatin; C038762:disodium hexachloroplatinate