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Bryan AM, Lin CY, Sorai M, et al. Measurement of extreme hyperfine fields in two-coordinate high-spin Fe2+ complexes by Mössbauer spectroscopy: essentially free-ion magnetism in the solid state. Inorg Chem. 2014;53(22):12100-7doi: 10.1021/ic501925e.
Bryan, A. M., Lin, C. Y., Sorai, M., Miyazaki, Y., Hoyt, H. M., Hablutzel, A., LaPointe, A., Reiff, W. M., Power, P. P., & Schulz, C. E. (2014). Measurement of extreme hyperfine fields in two-coordinate high-spin Fe2+ complexes by Mössbauer spectroscopy: essentially free-ion magnetism in the solid state. Inorganic chemistry, 53(22), 12100-7. https://doi.org/10.1021/ic501925e
Bryan, Aimee M, et al. "Measurement of extreme hyperfine fields in two-coordinate high-spin Fe2+ complexes by Mössbauer spectroscopy: essentially free-ion magnetism in the solid state." Inorganic chemistry vol. 53,22 (2014): 12100-7. doi: https://doi.org/10.1021/ic501925e
Bryan AM, Lin CY, Sorai M, Miyazaki Y, Hoyt HM, Hablutzel A, LaPointe A, Reiff WM, Power PP, Schulz CE. Measurement of extreme hyperfine fields in two-coordinate high-spin Fe2+ complexes by Mössbauer spectroscopy: essentially free-ion magnetism in the solid state. Inorg Chem. 2014 Nov 17;53(22):12100-7. doi: 10.1021/ic501925e. Epub 2014 Nov 04. PMID: 25368962.
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Inorg Chem. 2014 Nov 17;53(22):12100-7. doi: 10.1021/ic501925e. Epub 2014 Nov 04.

Measurement of extreme hyperfine fields in two-coordinate high-spin Fe2+ complexes by Mössbauer spectroscopy: essentially free-ion magnetism in the solid state.

Inorganic chemistry

Aimee M Bryan, Chun-Yi Lin, Michio Sorai, Yuji Miyazaki, Helen M Hoyt, Annelise Hablutzel, Anne LaPointe, William M Reiff, Philip P Power, Charles E Schulz

Affiliations

  1. Department of Chemistry, University of California at Davis , Davis, California 95616, United States.

PMID: 25368962 DOI: 10.1021/ic501925e

Abstract

Mössbauer studies of three two-coordinate linear high-spin Fe(2+) compounds, namely, Fe{N(SiMe3)(Dipp)}2 (1) (Dipp = C6H3-2,6-(i)Pr2), Fe(OAr')2 (2) [Ar' = C6H3-2,6-(C6H3-2,6-(i)Pr2)2], and Fe{C(SiMe3)3}2 (3), are presented. The complexes were characterized by zero- and applied-field Mössbauer spectroscopy (1-3), as well as zero- and applied-field heat-capacity measurements (3). As 1-3 are rigorously linear, the distortion(s) that might normally be expected in view of the Jahn-Teller theorem need not necessarily apply. We find that the resulting very large unquenched orbital angular momentum leads to what we believe to be the largest observed internal magnetic field to date in a high-spin iron(II) compound, specifically +162 T in 1. The latter field is strongly polarized along the directions of the external field for both longitudinal and transverse field applications. For the longitudinal case, the applied field increases the overall hyperfine splitting consistent with a dominant orbital contribution to the effective internal field. By contrast, 2 has an internal field that is not as strongly polarized along a longitudinally applied field and is smaller in magnitude at ca. 116 T. Complex 3 behaves similarly to complex 1. They are sufficiently self-dilute (e.g., Fe···Fe distances of ca. 9-10 Å) to exhibit varying degrees of slow paramagnetic relaxation in zero field for the neat solid form. In the absence of EPR signals for 1-3, we show that heat-capacity measurements for one of the complexes (3) establish a geff value near 12, in agreement with the principal component of the ligand electric field gradient being coincident with the z axis.

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