Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy

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Solution-phase photoinduced low-spin to high-spin conversion in the FeII polypyridyl complex [Fe(tren(py)3)]2+ (where tren(py)3 is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following 1A1 --> 1MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L2- and L3-edges were observed concomitant with formation of the transient high-spin 5T2 state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p ... continued below

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Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey; McCusker, James K.; de Groot, Frank M. F. & Schoenlein, Robert W. April 30, 2010.

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Solution-phase photoinduced low-spin to high-spin conversion in the FeII polypyridyl complex [Fe(tren(py)3)]2+ (where tren(py)3 is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following 1A1 --> 1MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L2- and L3-edges were observed concomitant with formation of the transient high-spin 5T2 state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 Angstrom increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

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  • Journal Name: Journal of the American Chemical Society; Journal Volume: 132; Journal Issue: 19; Related Information: Journal Publication Date: May 19, 2010

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  • Report No.: LBNL-3343E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 983208
  • Archival Resource Key: ark:/67531/metadc1014901

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  • April 30, 2010

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  • Oct. 14, 2017, 8:36 a.m.

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  • Oct. 17, 2017, 6:25 p.m.

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Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey; McCusker, James K.; de Groot, Frank M. F. & Schoenlein, Robert W. Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy, article, April 30, 2010; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc1014901/: accessed November 13, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.