Vanadium(II) heptacyanomolybdate(III)-based magnet exhibiting a high Curie temperature of 110 K

Inorganic Chemistry

Volumn 49, Issue 4, 2010, Pages 1298-1300

  Tomono, Keisuke ^a   Tsunobuchi, Yoshihide ^a   Nakabayashi, Koji ^a   Ohkoshi, Shin Ichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 77249147943     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic9022079     Document Type: Article

References (48)

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48. Reacting a deoxygenated aqueous solution of K4[Mo(CN)7] 32H2O (5-10-3 mol dm-3) with a deoxygenated aqueous solution of Mn-(NO3)2 3 6H2O (1-10-2 mol dm-3) containing pyrimidine (2-10-1 mol dm-3) in an H-shaped tube under an argon atmosphere gave a green-brown single crystal of MnMo. The IR spectrum had a CN stretching peak at 2084 cm-1. Single-crystal X-ray analysis of MnMo indicated that this compound belonged to the monoclinic structure of space group P21/n [a=7.20778 (13) A °, b = 15.7128 (3) A °, c = 18.1688 (3) A °, β = 95.0877(7)-, and Z = 4]. The structure was solved by direct methods and refined on F2 to R1 (wR2) = 0.0196 (0.0631) using 4365 reflections with F2 > 2.0σ (F2) (Table S1 in the Supporting Information). The non-H atoms were anisotropically refined. The H atoms of pyrimidine and water were refined isotropically. The asymmetric unit consisted of a [Mo(CN)7]4-anion, a [Mn1-(pyrimidine)(H2O)]2+ cation, half of a [Mn2(pyrimidine)2]2+ cation, and half of a [Mn3(H2O)2]2+ cation (Figure S1 in the Supporting Information). The broadening of the XRD pattern in VMo is considered to be due to the low crystallinity derived from the lack of V2+ and [Mo(CN)7]4-from the lattice. The defects will be occupied by water molecules, resulting in the number of water molecules on VMo being higher than that of MnMo. Five batches of VMo synthesis under the same reaction conditions showed the same magnetic properties, indicating that the present VMo can be obtained reproducibly. This MS value of VMo is closed to the expected saturation value of 5.0 μ B, assuming that this compound is a ferrimagnet with antiferromagnetic interaction between VII (S=3/2) and MoIII (S=1/2). This difference ofMS values may be due to the low crystallinity of the prepared sample.