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  Slow magnetization dynamics in a series of two-coordinate iron(II) complexes

Zadrozny, J. M., Atanasov, M., Bryan, A. M., Lin, C.-Y., Rekken, B. D., Power, P. P., et al. (2013). Slow magnetization dynamics in a series of two-coordinate iron(II) complexes. Chemical Science, 4(1), 125-138. doi:10.1039/C2SC20801F.

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Zadrozny, Joseph M.1, Author
Atanasov, Mihail2, 3, Author              
Bryan, Aimee M.4, Author
Lin, Chun-Yi4, Author
Rekken, Brian D.4, Author
Power, Philip P.4, Author
Neese, Frank2, Author              
Long, Jeffrey R.1, Author
Affiliations:
1Department of Chemistry, University of California, Berkeley, California, USA, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
3Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad Georgi Bontchev Str. 11, 1113 Sofia, Bulgaria, ou_persistent22              
4Department of Chemistry, University of California, Davis, California, USA, ou_persistent22              

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 Abstract: A series of two-coordinate complexes of iron(II) were prepared and studied for single-molecule magnet behavior. Five of the compounds, Fe[N(SiMe3)(Dipp)]2 (1), Fe[C(SiMe3)3]2 (2), Fe[N(H)Ar′]2 (3), Fe[N(H)Ar*]2 (4), and Fe(OAr′)2 (5) feature a linear geometry at the FeII center, while the sixth compound, Fe[N(H)Ar#]2 (6), is bent with an N–Fe–N angle of 140.9(2)° (Dipp = C6H3-2,6-Pri2; Ar′ = C6H3-2,6-(C6H3-2,6-Pri2)2; Ar* = C6H3-2,6-(C6H2-2,4,6-Pri2)2; Ar# = C6H3-2,6-(C6H2-2,4,6-Me3)2). Ac magnetic susceptibility data for all compounds revealed slow magnetic relaxation under an applied dc field, with the magnetic relaxation times following a general trend of 1 > 2 > 3 > 4 > 5 ≫ 6. Arrhenius plots created for the linear complexes were fit by employing a sum of tunneling, direct, Raman, and Orbach relaxation processes, resulting in spin reversal barriers of Ueff = 181, 146, 109, 104, and 43 cm−1 for 1–5, respectively. CASSCF/NEVPT2 calculations on the crystal structures were performed to explore the influence of deviations from rigorous D∞h geometry on the d-orbital splittings and the electronic state energies. Asymmetry in the ligand fields quenches the orbital angular momentum of 1–6, but ultimately spin–orbit coupling is strong enough to compensate and regenerate the orbital moment. The lack of simple Arrhenius behavior in 1–5 can be attributed to a combination of the asymmetric ligand field and the influence of vibronic coupling, with the latter possibility being suggested by thermal ellipsoid models to the diffraction data.

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Language(s): eng - English
 Dates: 2012-06-232012-10-252013-01-01
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C2SC20801F
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Title: Chemical Science
  Abbreviation : Chem. Sci.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 4 (1) Sequence Number: - Start / End Page: 125 - 138 Identifier: ISSN: 2041-6520
CoNE: https://pure.mpg.de/cone/journals/resource/2041-6520