Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States
Abstract
The sign and intensity of photoinduced electron spin polarization (ESP) in the electronic ground doublet states (2So/Do) of chromophore-radical complexes can be controlled by changing the nature of the metal ion. The complexes consist of an organic radical (nitronylnitroxide, NN) covalently attached to a donor acceptor chromophore via a meta-phenylene bridge, (bpy)M(CAT-m-Ph-NN) (1) (bpy = 4,4’-di-tert-butyl-2,2’-bipyridine, M = PdII (1-Pd) or PtII (1-Pt), CAT = 3-tert-butylcatecholate, m-Ph = meta-phenylene). In both complexes, photoexcitation with visible light pro-duces an initial exchange-coupled, 3-spin (bpy•-, CAT+• = semiquinone (SQ) and NN•), charge-separated doublet 2S1 (S = chromophore excited spin singlet configuration) excited state that rapidly decays to the ground state via a 2T1 (T = chromophore excited spin triplet configuration) state. This process is not expected to be spin selective and only very weak emissive ESP is found for 1-Pd. In contrast, strong absorptive ESP is generated in 1-Pt. Furthermore, it is postulated that zero-field splitting induced transitions between the chromophoric 2T1 and 4T1 states (1-Pd and 1-Pt) and spin-orbit induced transitions between 2T1 and NN-based quartet states (1-Pt) ac-count for the differences in polarization.
- Authors:
-
[1];
[2];
[3]
- Univ. of New Mexico, Albuquerque, NM (United States)
- North Carolina State Univ., Raleigh, NC (United States)
- Brock Univ., Ontario, (Canada)
- Publication Date:
- Research Org.:
- North Carolina State University, Raleigh, NC (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1830693
- Grant/Contract Number:
- SC0020199
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 28; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chromophores; Energy; Quantum mechanics; Polarization; Excited states
Citation Formats
Kirk, Martin L., Shultz, David A., Chen, Ju, Hewitt, Patrick, Daley, David, Paudel, Sangita, and van der Est, Art. Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States. United States: N. p., 2021.
Web. doi:10.1021/jacs.1c04149.
Kirk, Martin L., Shultz, David A., Chen, Ju, Hewitt, Patrick, Daley, David, Paudel, Sangita, & van der Est, Art. Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States. United States. https://doi.org/10.1021/jacs.1c04149
Kirk, Martin L., Shultz, David A., Chen, Ju, Hewitt, Patrick, Daley, David, Paudel, Sangita, and van der Est, Art. Mon .
"Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States". United States. https://doi.org/10.1021/jacs.1c04149. https://www.osti.gov/servlets/purl/1830693.
@article{osti_1830693,
title = {Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States},
author = {Kirk, Martin L. and Shultz, David A. and Chen, Ju and Hewitt, Patrick and Daley, David and Paudel, Sangita and van der Est, Art},
abstractNote = {The sign and intensity of photoinduced electron spin polarization (ESP) in the electronic ground doublet states (2So/Do) of chromophore-radical complexes can be controlled by changing the nature of the metal ion. The complexes consist of an organic radical (nitronylnitroxide, NN) covalently attached to a donor acceptor chromophore via a meta-phenylene bridge, (bpy)M(CAT-m-Ph-NN) (1) (bpy = 4,4’-di-tert-butyl-2,2’-bipyridine, M = PdII (1-Pd) or PtII (1-Pt), CAT = 3-tert-butylcatecholate, m-Ph = meta-phenylene). In both complexes, photoexcitation with visible light pro-duces an initial exchange-coupled, 3-spin (bpy•-, CAT+• = semiquinone (SQ) and NN•), charge-separated doublet 2S1 (S = chromophore excited spin singlet configuration) excited state that rapidly decays to the ground state via a 2T1 (T = chromophore excited spin triplet configuration) state. This process is not expected to be spin selective and only very weak emissive ESP is found for 1-Pd. In contrast, strong absorptive ESP is generated in 1-Pt. Furthermore, it is postulated that zero-field splitting induced transitions between the chromophoric 2T1 and 4T1 states (1-Pd and 1-Pt) and spin-orbit induced transitions between 2T1 and NN-based quartet states (1-Pt) ac-count for the differences in polarization.},
doi = {10.1021/jacs.1c04149},
journal = {Journal of the American Chemical Society},
number = 28,
volume = 143,
place = {United States},
year = {Mon Jul 12 00:00:00 EDT 2021},
month = {Mon Jul 12 00:00:00 EDT 2021}
}
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