Mapping
the UV Photophysics of Platinum Metal Complexes
Bound to Nucleobases: Laser Spectroscopy of Isolated Uracil·Pt(CN)<sub>4</sub><sup>2–</sup> and Uracil·Pt(CN)<sub>6</sub><sup>2–</sup> Complexes
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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<sup>IV</sup>(CN)<sub>6</sub><sup>2–</sup>·Ur and Pt<sup>II</sup>(CN)<sub>4</sub><sup>2–</sup>·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 (λ<sub>max</sub> = 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<sup>IV</sup>(CN)<sub>6</sub><sup>2–</sup>·Ur photoexcitation resulting in complex
fission, while Pt<sup>II</sup>(CN)<sub>4</sub><sup>2–</sup>·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