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Volumn 36, Issue 20, 1997, Pages 4347-4359

The Valence-Detrapping Phase Transition in a Crystal of the Mixed-Valence Trinuclear Iron Cyanoacetate Complex [Fe3O(O2CCH2CN)6(H 2O)3]

Author keywords

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Indexed keywords


EID: 0001363313     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic961438w     Document Type: Article
Times cited : (68)

References (76)
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    • note
    • -1 under 100 kW operation at F-24 of the TRIGA II nuclear reactor at Atomic Energy Institute of Rikkyo University. Commercially purchased standard solutions of Fe and Co (1000 ppm, Wako) for atomic absorption photo spec trome try were used as the references.
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    • Unpublished data
    • w = 0.0503, 0.0732; Fe⋯Fe = 3.325(1), 3.327-(1), 3.328(1) Å.
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    • note
    • (a) Though all of the R3̄ structures were solved by the hexagonal setting, the constants are shown with respect to the rhombohedral setting in Tables 1 and 2 for easy comparison,
  • 46
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    • r as described in International Tables for Crystallography (Hahn, T., Ed.; Kluwer Academic Publishers: Dordrecht, 1992; 3rd revised ed., Vol. A, p 77), Indeed, a systematic search for the unit cell of the highest possible Laue symmetry using TRACER-II described by Lawton (Lawton, S. L. J. Appl. Crystallogr. 1973, 6, 309) was carried out for each complex, and the presence of a unit cell of higher Laue symmetry, cubic I, was indicated with a tolerance factor of 0.5. However, the Laue symmetry check for the cubic I cells indicated that even the lowest Laue symmetry of cubic system m3̄ was not accepted. Consequently, the crystal systems of these complexes have been settled into rhombohedral, neither cubic nor tetragonal.
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    • r as described in International Tables for Crystallography (Hahn, T., Ed.; Kluwer Academic Publishers: Dordrecht, 1992; 3rd revised ed., Vol. A, p 77), Indeed, a systematic search for the unit cell of the highest possible Laue symmetry using TRACER-II described by Lawton (Lawton, S. L. J. Appl. Crystallogr. 1973, 6, 309) was carried out for each complex, and the presence of a unit cell of higher Laue symmetry, cubic I, was indicated with a tolerance factor of 0.5. However, the Laue symmetry check for the cubic I cells indicated that even the lowest Laue symmetry of cubic system m3̄ was not accepted. Consequently, the crystal systems of these complexes have been settled into rhombohedral, neither cubic nor tetragonal.
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    • note
    • When the temperature is lowered from 135 to 100 K, at first sight the most important change appears as a shrinkage of the a axis by 0.121 Å from 12.215 Å (135 K) to 12.094 Å (100 K) whereas b and c axes show only smaller shrinkages of 0.033 and 0.007 Å, respectively, although those changes are caused by a different axis choice of unit cell at each temperature. In the triclinic crystal system, a unit cell must be chosen such that the a, b, and c axes are the shortest, whereas in the rhombohedral crystal system a unit cell must be chosen such that the 3-fold axis becomes a body-diagonal axis even if the 3-fold axis is shorter than the a axis. Owing to these agreements, the triclinic a axis at 100 K corresponds to the body-diagonal axis of the rhombohedral cell above 135 K in the present case. If the triclinic axes are transformed to correspond to the rhombohedral axes above 135 K by using a transformation matrix, the cell constants at 100 K are given as follows: a' = 12.176(2) Å, b' = 12.182(3) Å, c' = 12.208(3) Å, ά = 110.04(2)°, β' = 109.95-(2)°, and γ' = 108.90(2)°. The constants with a' ≅ b' < c' and α' ≅ β' > γ ' within 3σ clearly indicate a slight but significant distortion from the rhombohedral cell.
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    • These spectra were obtained from the samples used in the heat-capacity measurement, and they are very slightly different from those previously presented in ref 15.
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    • Tabulated heat-capacity data of these complexes are available as Supporting Information.
    • Tabulated heat-capacity data of these complexes are available as Supporting Information.
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    • Unpublished
    • Unpublished.


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