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Mapping the UV photophysics of platinum metal complexes bound to nucleobases: Laser spectroscopy of isolated Uracil·pt(CN)42- and Uracil·Pt(CN)62- complexes

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JournalJOURNAL OF PHYSICAL CHEMISTRY LETTERS
DatePublished - 2 Oct 2014
Issue number19
Volume5
Number of pages5
Pages (from-to)3281-3285
Original languageEnglish

Abstract

We report the first UV laser spectroscopic study of isolated gas-phase complexes of platinum metal complex anions bound to a nucleobase as model systems for exploring at the molecular level the key photophysical processes involved in photodynamic therapy. Spectra of the PtIV(CN)62-·Ur and PtII(CN)42-·Ur complexes were acquired across the 220-320 nm range using mass-selective photodepletion and photofragment action spectroscopy. The spectra of both complexes reveal prominent UV absorption bands (max = 4.90 and 4.70 eV) that we assign primarily to excitation of the Ur localized chromophore. Distinctive UV photofragmentation products are observed for the complexes, with PtIV(CN)62-·Ur photoexcitation resulting in complex fission, while PtII(CN)42-·Ur photoexcitation initiates a nucleobase proton-transfer reaction across 4.4-5.2 eV and electron detachment above 5.2 eV. The observed photofragments are consistent with ultrafast decay of a Ur localized excited state back to the electronic ground state followed by intramolecular vibrational relaxation and ergodic complex fragmentation.

    Research areas

  • laser photodissociation, multiply charged anions, nucleobase photochemistry, photodynamic therapy, Pt complex photochemistry, uracil photophysics

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