Direct determination of the single-ion anisotropy in a one-dimensional magnetic system by high-field EPR spectroscopy; synthesis, EPR, and X-ray structure of NixZn1-x(C2O4)(dmiz)2.
The synthesis, X-ray structure, and EPR measurements of the integer-spin linear-chain antiferromagnet [Ni(ox)(dmiz)2] (where ox = C2O4(2-) and dmiz = 1,2-dimethylimidazole) are presented. The sign and size of the single-ion zero field splitting (Zfs) of the divalent Ni have been determined by high field/high-frequency EPR spectroscopy. The spectra of powder samples of the derivatives [NixZn1-x(C2O4)(dmiz)2] for x = 0.09 and 0.07, at frequencies ranging from 110 to 440 GHz allowed the accurate determination of the zfs parameters D and E, with D = 1.875(4) cm(-1) and E = 0.38 cm(-1). The X-ray structure has been determined from measurements on a single crystal with x = 0.07. Structural parameters are as follows: a = 14.5252(7) A, b = 12.1916(8) A, c = 8.6850(8) A,beta = 97.460(6)degrees in space group C2/c. The zigzag chain contains octahedrally coordinated metal ions with two cis-oriented N-coordinated dmiz ligands and two cis-oriented, tetradentate bridging oxalato(2-) ligands, together resulting in a MN2O4 donor set. The structure was refined to a conventional R value of 0.073 for 1,051 observed reflections. Zn-O distances are 2.167(5) A and Zn-N = 2.098 A. Coordination angles vary for cis angles from 78.4 to 100.7 degrees, with trans angles varying from 163.9 degrees to 165.5 degrees.
Pardi
L A
LA
National High Magnetic Field Laboratory, Tallahassee, Florida, USA.
Hassan
A K
AK
Hulsbergen
F B
FB
Reedijk
J
J
Spek
A L
AL
Brunel
L C
LC