Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States

Kirk, Martin L.; Shultz, David A.; Chen, Ju; Hewitt, Patrick; Daley, David; Paudel, Sangita; van der Est, Art

doi:10.1021/jacs.1c04149

Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States

Journal Article · Mon Jul 12 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c04149· OSTI ID:1830693

^[1]; ^[2]; Chen, Ju ^[3]; Hewitt, Patrick ^[2]; Daley, David ^[2]; Paudel, Sangita ^[3]; ^[4]

Univ. of New Mexico, Albuquerque, NM (United States); North Carolina State University
North Carolina State Univ., Raleigh, NC (United States)
Univ. of New Mexico, Albuquerque, NM (United States)
Brock Univ., Ontario, (Canada)

The sign and intensity of photoinduced electron spin polarization (ESP) in the electronic ground doublet states (²S_o/D_o) 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 = Pd^II (1-Pd) or Pt^II (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.

View Accepted Manuscript (DOE)

Research Organization:: North Carolina State Univ., Raleigh, NC (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0020199

OSTI ID:: 1830693

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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