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Cited by 579

The DOI matches its Crossref record; 42 of the 42 references it cites were found in a registry or an index.

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

Zadrozny, Joseph M., Atanasov, Mihail, Bryan, Aimee M., Lin, Chun-Yi, Rekken, Brian D., Power, Philip P., Neese, Frank, Long, Jeffrey R.·2013·Chem. Sci.
DOI 10.1039/c2sc20801f
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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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Metadata

Authors
Zadrozny, J. M., Atanasov, M., Bryan, A. M., Lin, C.-Y., Rekken, B. D., Power, P. P., Neese, F., & Long, J. R.
Venue
Chem. Sci.
Publisher
Royal Society of Chemistry (RSC)
Published
2013
Volume
4
Issue
1
Pages
125-138
ISSN
  • 2041-6520 (ISSN-L)
  • 2041-6539
DOI
10.1039/c2sc20801f
OpenAlex
W1992996545
Cited by
579
References
42
FWCI
19.31
Type
journal article
Language
en
Open access
closed

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