Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution
112 - 120
Chemical Physics Letters
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We report the results of ultrafast transient absorption studies of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt 2 (μ-P 2 O 5 H 2 ) 4 ] 4− (Pt(pop)) and its perfluoroborated derivative [Pt 2 (μ-P 2 O 5 (BF 2 ) 4 ] 4− (Pt(pop-BF 2 )) in water and acetonitrile upon excitation of high lying ( < 300 nm) UV absorption bands. We observe an ultrafast relaxation channel from high lying states to the lowest triplet state that partly (Pt(pop) in H 2 O, Pt(pop-BF 2 )) or fully (Pt(pop) in MeCN) bypasses the lowest singlet excited state. As a consequence, vibrational wave packets are detected in the lowest triplet state and/or the lowest excited singlet of both complexes, even though the electronic relaxation cascade spans ca. 2 and 1.3 eV, respectively. In the case of Pt(pop-BF 2 ), coherent wave packets generated by optical excitation of the lowest singlet 1 A 2u state also are reported. Overall, the reported dephasing times of the Pt-Pt oscillator in the ground, singlet and triplet states do not depend much on the solvent or the molecular structure.
AuthorsMonni, R; Auböck, G; Kinschel, D; Aziz-Lange, KM; Gray, HB; Vlček, A; Chergui, M
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