DC Field | Value | Language |
---|---|---|
dc.contributor.author | Huse, Nils | ko |
dc.contributor.author | Kim, Tae Kyu | ko |
dc.contributor.author | Jamula, Lindsey | ko |
dc.contributor.author | McCusker, James K. | ko |
dc.contributor.author | de Groot, Frank M. F. | ko |
dc.contributor.author | Schoenlein, Robert W. | ko |
dc.date.accessioned | 2024-03-05T09:00:28Z | - |
dc.date.available | 2024-03-05T09:00:28Z | - |
dc.date.created | 2024-02-28 | - |
dc.date.issued | 2010-05 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.132, no.19, pp.6809 - 6816 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/318415 | - |
dc.description.abstract | Solution-phase photoinduced low-spin to high-spin conversion in the Fe-II 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 (1)A(1) -> (MLCT)-M-1 (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L-2- and L-3-edges were observed concomitant with formation of the transient high-spin T-5(2) 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 similar to 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 a-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. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy | - |
dc.type | Article | - |
dc.identifier.wosid | 000277721500041 | - |
dc.identifier.scopusid | 2-s2.0-77952386780 | - |
dc.type.rims | ART | - |
dc.citation.volume | 132 | - |
dc.citation.issue | 19 | - |
dc.citation.beginningpage | 6809 | - |
dc.citation.endingpage | 6816 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/ja101381a | - |
dc.contributor.localauthor | Kim, Tae Kyu | - |
dc.contributor.nonIdAuthor | Huse, Nils | - |
dc.contributor.nonIdAuthor | Jamula, Lindsey | - |
dc.contributor.nonIdAuthor | McCusker, James K. | - |
dc.contributor.nonIdAuthor | de Groot, Frank M. F. | - |
dc.contributor.nonIdAuthor | Schoenlein, Robert W. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | L-EDGE | - |
dc.subject.keywordPlus | ABSORPTION-SPECTROSCOPY | - |
dc.subject.keywordPlus | DYNAMICS | - |
dc.subject.keywordPlus | BAND | - |
dc.subject.keywordPlus | IRON | - |
dc.subject.keywordPlus | FE | - |
dc.subject.keywordPlus | SPECTRA | - |
dc.subject.keywordPlus | XANES | - |
dc.subject.keywordPlus | SITES | - |
dc.subject.keywordPlus | WATER | - |
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