Valence trapping of mixed-valence [Fe3O(O2CCH3)6(py) 3]·S (S = solvent) complexes at high pressure

James K. McCusker, Ho Gyeom Jang, Maruta Zvagulis, Walter Ley, Harry G. Drickamer, David N. Hendrickson

Research output: Contribution to journalArticle

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Abstract

The transformation from valence detrapped to valence trapped for two oxo-centered trinuclear iron acetate complexes is studied at pressures up to 95 kbar with the use of a diamond anvil cell. Variable-pressure 57Fe Mössbauer spectra are presented for 57Fe-enriched [Fe3O(O2CCH3)6(py) 3]·py (1) and [Fe3O(O2CCH3)6(py) 3]·CHCl3 (2), where py is pyridine. At 298 K and applied pressures less than ∼20 kbar, each of the complexes gives a spectrum with a single quadrupole-split doublet, which indicates that complexes 1 and 2 are interconverting faster than the Mössbauer time scale under these conditions. Application of pressure in excess of ∼80 kbar leads to both complexes becoming valence trapped, as indicated by two doublets in the Mössbauer spectrum with an area ratio of ∼2:1 (FeIII:FeII). At intermediate pressures, each of these complexes gives a Mössbauer spectrum that can be fit as a superposition of a valence detrapped doublet and a valence trapped four-line pattern. The nature of the pressure-induced transformations observed in complexes 1 and 2 is discussed with reference to the phase diagram derived from a spin-Hamiltonian theoretical approach that parametrizes intermolecular interactions in terms of the molecular field approximation.

Original languageEnglish
Pages (from-to)1985-1990
Number of pages6
JournalInorganic Chemistry
Volume30
Issue number9
Publication statusPublished - 1991 Dec 1
Externally publishedYes

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trapping
valence
Pressure
Hamiltonians
Diamond
anvils
Phase diagrams
acetates
pyridines
Acetates
Iron
quadrupoles
diamonds
phase diagrams
iron
cells
approximation
interactions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

McCusker, J. K., Jang, H. G., Zvagulis, M., Ley, W., Drickamer, H. G., & Hendrickson, D. N. (1991). Valence trapping of mixed-valence [Fe3O(O2CCH3)6(py) 3]·S (S = solvent) complexes at high pressure. Inorganic Chemistry, 30(9), 1985-1990.

Valence trapping of mixed-valence [Fe3O(O2CCH3)6(py) 3]·S (S = solvent) complexes at high pressure. / McCusker, James K.; Jang, Ho Gyeom; Zvagulis, Maruta; Ley, Walter; Drickamer, Harry G.; Hendrickson, David N.

In: Inorganic Chemistry, Vol. 30, No. 9, 01.12.1991, p. 1985-1990.

Research output: Contribution to journalArticle

McCusker, JK, Jang, HG, Zvagulis, M, Ley, W, Drickamer, HG & Hendrickson, DN 1991, 'Valence trapping of mixed-valence [Fe3O(O2CCH3)6(py) 3]·S (S = solvent) complexes at high pressure', Inorganic Chemistry, vol. 30, no. 9, pp. 1985-1990.
McCusker JK, Jang HG, Zvagulis M, Ley W, Drickamer HG, Hendrickson DN. Valence trapping of mixed-valence [Fe3O(O2CCH3)6(py) 3]·S (S = solvent) complexes at high pressure. Inorganic Chemistry. 1991 Dec 1;30(9):1985-1990.
McCusker, James K. ; Jang, Ho Gyeom ; Zvagulis, Maruta ; Ley, Walter ; Drickamer, Harry G. ; Hendrickson, David N. / Valence trapping of mixed-valence [Fe3O(O2CCH3)6(py) 3]·S (S = solvent) complexes at high pressure. In: Inorganic Chemistry. 1991 ; Vol. 30, No. 9. pp. 1985-1990.
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abstract = "The transformation from valence detrapped to valence trapped for two oxo-centered trinuclear iron acetate complexes is studied at pressures up to 95 kbar with the use of a diamond anvil cell. Variable-pressure 57Fe M{\"o}ssbauer spectra are presented for 57Fe-enriched [Fe3O(O2CCH3)6(py) 3]·py (1) and [Fe3O(O2CCH3)6(py) 3]·CHCl3 (2), where py is pyridine. At 298 K and applied pressures less than ∼20 kbar, each of the complexes gives a spectrum with a single quadrupole-split doublet, which indicates that complexes 1 and 2 are interconverting faster than the M{\"o}ssbauer time scale under these conditions. Application of pressure in excess of ∼80 kbar leads to both complexes becoming valence trapped, as indicated by two doublets in the M{\"o}ssbauer spectrum with an area ratio of ∼2:1 (FeIII:FeII). At intermediate pressures, each of these complexes gives a M{\"o}ssbauer spectrum that can be fit as a superposition of a valence detrapped doublet and a valence trapped four-line pattern. The nature of the pressure-induced transformations observed in complexes 1 and 2 is discussed with reference to the phase diagram derived from a spin-Hamiltonian theoretical approach that parametrizes intermolecular interactions in terms of the molecular field approximation.",
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AB - The transformation from valence detrapped to valence trapped for two oxo-centered trinuclear iron acetate complexes is studied at pressures up to 95 kbar with the use of a diamond anvil cell. Variable-pressure 57Fe Mössbauer spectra are presented for 57Fe-enriched [Fe3O(O2CCH3)6(py) 3]·py (1) and [Fe3O(O2CCH3)6(py) 3]·CHCl3 (2), where py is pyridine. At 298 K and applied pressures less than ∼20 kbar, each of the complexes gives a spectrum with a single quadrupole-split doublet, which indicates that complexes 1 and 2 are interconverting faster than the Mössbauer time scale under these conditions. Application of pressure in excess of ∼80 kbar leads to both complexes becoming valence trapped, as indicated by two doublets in the Mössbauer spectrum with an area ratio of ∼2:1 (FeIII:FeII). At intermediate pressures, each of these complexes gives a Mössbauer spectrum that can be fit as a superposition of a valence detrapped doublet and a valence trapped four-line pattern. The nature of the pressure-induced transformations observed in complexes 1 and 2 is discussed with reference to the phase diagram derived from a spin-Hamiltonian theoretical approach that parametrizes intermolecular interactions in terms of the molecular field approximation.

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