期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 13, 页码 4691-4696出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b01101
关键词
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资金
- Air Force Office of Scientific Research [FA9550-14-1-0314]
Iron porphyrins are the active sites of many natural and artificial catalysts, and their photoinduced dynamics have been described as either relaxation into a vibrationally hot ground state or as a cascade through metal-centered states. In this work, we directly probe the metal center of iron(III) tetraphenyl porphyrin chloride (FeTPPC1) using femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy. Photoexcitation at 400 nm produces a (pi,pi*) state that evolves in 70 fs to an iron(II) ligand-to-metal charge transfer (LMCT) state. The LMCT state relaxes to a vibrationally hot ground state in 1.13 ps, without involvement of (d,d) intermediates. The tabletop extreme ultraviolet probe, combined with semiempirical ligand field multiplet calculations, dearly distinguishes between metal-centered and ligand-centered excited states and resolves competing accounts of Fe(III) porphyrin relaxation. This work introduces tabletop M-edge XANES as a valuable tool for measuring femtosecond dynamics of molecular transition metal complexes in the condensed phase.
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