Mapping the UV Photophysics of Platinum Metal Complexes Bound to Nucleobases: Laser Spectroscopy of Isolated Uracil·Pt(CN)4(2-) and Uracil·Pt(CN)6(2-) Complexes.

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 Pt(IV)(CN)6(2-)·Ur and Pt(II)(CN)4(2-)·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 (λmax = 4.90 and 4.70 eV) that we assign primarily to excitation of the Ur π-π* localized chromophore. Distinctive UV photofragmentation products are observed for the complexes, with Pt(IV)(CN)6(2-)·Ur photoexcitation resulting in complex fission, while Pt(II)(CN)4(2-)·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.