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Ultrafast Photodynamics of an Azopyridine-Functionalized Iron(II) Complex: Implications on the Concept of Ligand-Driven Light-Induced Spin Change.

08:00 EDT 24th September 2019 | BioPortfolio

Summary of "Ultrafast Photodynamics of an Azopyridine-Functionalized Iron(II) Complex: Implications on the Concept of Ligand-Driven Light-Induced Spin Change."

We report on the ultrafast photodynamics of an iron(II) complex with a photo-isomerizable pentadentate azo-tetrapyridylamino ligand after irradiation with ultraviolet (UV) light. The results of femtosecond transient electronic absorption spectroscopy (TEAS) performed on the low-spin (LS) form of the title complex show that initial excitation of the ππ* state of the azopyridine unit in the ligand at λ = 312 nm is followed by an ultrafast intersystem crossing (ISC) that leads to the formation of a metal-centered (MC) T state, in competition with the intended photoswitching of the azopyridine unit. Additional measurements carried out upon excitation of the singlet metal-to-ligand charge transfer (MLCT) transition at λ = 455 nm suggest that this energy transfer occurs via a MLCT state. The resulting high-spin (HS) T state of the complex is metastable and recovers to the LS ground state with a time constant of ~3 ns. The implications of these observations on the LD-LISC (ligand-driven light-induced spin change) concept are discussed.

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Name: The journal of physical chemistry letters
ISSN: 1948-7185
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