“…We ascribe this to relaxation broadening effects that commence above T N but that persist to temperatures below T N until the sample is fully ordered and magnetically saturated on a Mössbauer spectroscopy time scale. This phenomenon has previously been observed in the study of Fe(NH 4 )(SO 4 ) 2 ·12H 2 O and to a lesser extent K 3 Fe(CN) 6 …”
The synthesis and single-crystal structure of a new one-to-one charge-transfer salt, derived from decamethylferrocene and 2,3-dicyano-1,4-naphthoquinone, are described. [Fe(Cp*)2][DCNQ] crystallizes in the orthorhombic space group Pbca, with a = 17.3149(5) A, b = 14.6862(4) A, c = 21.0507(6) A, and Z = 8. Magnetization vs temperature data obtained in 100 G suggest that the compound exhibits dominant one-dimensional ferromagnetic coupling and that it subsequently undergoes an antiferromagnetic phase transition below TN approximately 4 K. Results of magnetization vs applied field experiments show that the compound is a metamagnet with a critical field of approximately 3 kG at 1.8 K. In the nominally antiferromagnetic state, apparent canting of the moments gives rise to a small amount of hysteresis. This picture is supported by ac susceptibility data. The 57Fe Mössbauer spectrum exhibits the expected decamethylferrocenium unresolved quadrupole doublet (delta = 0.53 mm/s) at 77 K and magnetic hyperfine splitting, Hint = 37.9 T, corresponding to long-range magnetic order at 1.63 K.
“…We ascribe this to relaxation broadening effects that commence above T N but that persist to temperatures below T N until the sample is fully ordered and magnetically saturated on a Mössbauer spectroscopy time scale. This phenomenon has previously been observed in the study of Fe(NH 4 )(SO 4 ) 2 ·12H 2 O and to a lesser extent K 3 Fe(CN) 6 …”
The synthesis and single-crystal structure of a new one-to-one charge-transfer salt, derived from decamethylferrocene and 2,3-dicyano-1,4-naphthoquinone, are described. [Fe(Cp*)2][DCNQ] crystallizes in the orthorhombic space group Pbca, with a = 17.3149(5) A, b = 14.6862(4) A, c = 21.0507(6) A, and Z = 8. Magnetization vs temperature data obtained in 100 G suggest that the compound exhibits dominant one-dimensional ferromagnetic coupling and that it subsequently undergoes an antiferromagnetic phase transition below TN approximately 4 K. Results of magnetization vs applied field experiments show that the compound is a metamagnet with a critical field of approximately 3 kG at 1.8 K. In the nominally antiferromagnetic state, apparent canting of the moments gives rise to a small amount of hysteresis. This picture is supported by ac susceptibility data. The 57Fe Mössbauer spectrum exhibits the expected decamethylferrocenium unresolved quadrupole doublet (delta = 0.53 mm/s) at 77 K and magnetic hyperfine splitting, Hint = 37.9 T, corresponding to long-range magnetic order at 1.63 K.
“…At 1.2 K (the low-temperature limit for our 4 He cryogenics system), critical spin fluctuations are apparently still sufficiently important as to lead to a highly broadened hyperfine pattern instead of the classical, resolved, narrow line-width, six transition pattern expected for magnetic saturation. The latter is observed for [Fe(CN) 6 ] 3- , which orders at ∼0.129 K with an internal field, H (0 K), of 194 kOe corresponding to a hyperfine splitting of ∼6.25 mm/s, which is comparable to the velocity span of the broad absorption pattern at 1.2 K. The Mössbauer spectroscopy results imply a T c ≈ 1.5 K for 2 , an order of magnitude greater than that found K 3 Fe(CN) 6 ], which contains “isolated” [Fe(CN) 6 ] 3- ions. 8 Temperature dependence of the 57 Fe Mössbauer spectra of 2 .…”
Diruthenium tetracarboxylates monocations are utilized as building blocks for cubic 3-D network structured molecule-based magnets. [Ru(II/III)(2)(O(2)CMe)(4)](3)[M(III)(CN)(6)] [M = Cr (1a), Fe (2), Co (3)] were prepared in aqueous solution. Powder X-ray diffraction indicates that they have body-centered cubic structures (space group = Imm, a = 13.34, 13.30, and 13.10 A for 1a, 2, and 3, respectively), which was confirmed for 1a by Reitveld analysis of the synchrotron powder data [a = 13.3756(5) A]. [Ru(2)(O(2)CMe)(4)](3)[M(III)(CN)(6)].xMeCN [M = Cr, x = 1.8 (1b); M = Mn, x = 3.3 (4)] were prepared from acetonitrile. The magnetic ordering of 1a (33 K), 1b (34.5 K), 2 (2.1 K), and 4 (9.6 K) was determined from the temperature dependencies of the in-phase (chi') alternating current (AC) susceptibility. The field dependence of the magnetization, M(H), at 2 K for 1a showed an unusual constricted hysteresis loop with a coercive field, H(cr), of 470 Oe while the M(H) data for 1b, 2, and 4 showed a normal hysteresis loop with a coercive field of 1670, 10, and 990 Oe, respectively. The (57)Fe Mössbauer spectrum of 2 is consistent with the presence of low spin Fe(III) (delta = -0.05 mm/s; DeltaE = 0.33 mm/s) at room temperature, and the onset of 3-D magnetic ordering at lower temperature (<2 K). The effects of M(III) in [M(III)(CN)(6)](3-), and the large zero-field splitting (D) of diruthenium tetracarboxylates are discussed. The increasing critical temperatures T(c), with increasing S could not be accounted for by mean field models without significantly different J values for 1a, 4, and 2. By fitting the T(c) data with mean field models [H = -2JS(Ru).(S(M) - micro(B)(g(Ru)S(Ru) + g(M)S(M))H], J/k(B) are 4.46, 1.90, and 0.70 K for 1a, 4, and 2, respectively.
“…Finally, we note that the Mössbauer spectrum at 1.37 K exhibits a small but definite quadrupolar shift (−0.33 mm s -1 ) which when considered as a small perturbation on the larger nuclear Zeeman splitting effect results in an internal hyperfine field H n ca. 49 T. This value for the trans -Cl 4 O 2 coordination of 2 is to be compared to the “all oxygen” coordinated FeNH 4 (SO 4 ) 2 ·12H 2 O, anhydrous Fe 2 (SO 4 ) 3 , and Fe(acetylacetonate) 3 for which H n = 58, 55, and 53 T, respectively, − and 44 T for the Cl 5 O chromophore of 1 . Thus, with increasing oxygen content in the coordination environment (“increasing ionicity”), one sees, at least qualitatively, the expected lessening of covalency reduction of H n…”
1,2-Diaminoethane (en) and FeCl3 give (enH2) [FeCl5(H2O)] (1) in concentrated HCl, extending the aquapentachloroferrate(III) series. For 1: C2H12N2Cl5OFe, orthorhombic, P2(1)2(1)2(1), a = 14.531(6) A, b = 10.772(4) A, c = 6.888(2) A, Z = 4. Diazabicyclo[2.2.2]octane dihydrochloride (DABCO-2HCl) and FeCl3 in concentrated HCl form a tetrachloroferrate(III) derivative whose subsequent ethanol treatment (restricted water access) results in the formation of a compound of composition (DABCOH2)2 [FeCl4(H2O)2]Cl3 (2). This contains the trans-[FeCl4(H2O)2](-) anion, in which the trans-Fe-O distances are 2.049(4) A. For 2: C12H32N4Cl7O2Fe, orthorhombic, Pnma, a = 16.378(3) A, b = 7.3323(6) A, c = 19.431(3) A, Z = 4. A combination of 57Fe Mössbauer spectroscopy and ac susceptibility data confirm uncanted 3D antiferromagnetic ground states with T(Néel) approximately 3.4 K for (enH2)[FeCl5(H2O)] and approximately 2.0 K for [DABCOH2]2[FeCl4(H2O)2]Cl3.
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