Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime.
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| Title: | Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime. |
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| Authors: | Kjær, Kasper Skov, Kaul, Nidhi, Prakash, Om, Chábera, Pavel, Rosemann, Nils W., Honarfar, Alireza, Gordivska, Olga, Fredin, Lisa A., Bergquist, Karl-Erik, Häggström, Lennart, Ericsson, Tore, Lindh, Linnea, Yartsev, Arkady, Styring, Stenbjörn, Huang, Ping, Uhlig, Jens, Bendix, Jesper, Strand, Daniel, Sundström, Villy, Persson, Petter |
| Source: | Science (pre-March 2025). 1/18/2019, Vol. 363 Issue 6424, p249-253. 5p. 1 Diagram, 1 Chart, 3 Graphs. |
| Subjects: | Charge transfer, Luminescence, Reactivity (Chemistry), Iron, Oxidation-reduction reaction, Carbenes, Ground state (Quantum mechanics) |
| Abstract: | Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation. The resulting complex [Fe(phtmeimb)2]+, where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)] borate}−, exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer (2LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the 2LMCTstate of [Fe(phtmeimb)2]+ in bimolecular quenching studies with methylviologen and diphenylamine. [ABSTRACT FROM AUTHOR] |
| Copyright of Science (pre-March 2025) is the property of American Association for the Advancement of Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Psychology and Behavioral Sciences Collection |
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| Abstract: | Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation. The resulting complex [Fe(phtmeimb)2]+, where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)] borate}−, exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer (2LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the 2LMCTstate of [Fe(phtmeimb)2]+ in bimolecular quenching studies with methylviologen and diphenylamine. [ABSTRACT FROM AUTHOR] |
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| ISSN: | 00368075 |
| DOI: | 10.1126/science.aau7160 |
