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Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State
Author(s) -
Iwamura Munetaka,
Fukui Airi,
Nozaki Koichi,
Kuramochi Hikaru,
Takeuchi Satoshi,
Tahara Tahei
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011813
Subject(s) - picosecond , excited state , trimer , intersystem crossing , chemistry , ultrafast laser spectroscopy , photochemistry , tetramer , intermolecular force , femtosecond , absorption spectroscopy , molecular physics , spectroscopy , dimer , atomic physics , molecule , laser , singlet state , optics , physics , organic chemistry , enzyme , quantum mechanics
Abstract Femtosecond time‐resolved absorption and picosecond time‐resolved emission measurements were carried out for highly concentrated aqueous solutions of K 2 [Pt(CN) 4 ] to investigate excited‐state dynamics of the [Pt(CN) 4 2− ] oligomers formed with metallophilic interactions. Time‐resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90‐ps and 400‐ps dynamics were assigned to the S 1 → T 1 intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency‐detected‐wavelength 2D analysis revealed that the 135‐cm −1 and 65‐cm −1 oscillations arise from the Pt–Pt stretch motions of the S 1 trimer and S 1 tetramer, respectively. The obtained time‐resolved spectroscopic data provide a clear view of the excited‐state dynamics of the [Pt(CN) 4 2− ] oligomers in the femto‐/picosecond time region.