High-spin molecules:: Synthesis, X-ray characterization, and magnetic behavior of two new cyano-bridged NII9MoV6 and NiII9WV6 clusters with a S=12 ground state

The preparations, X-ray structures, and magnetic characterizations are presented for two new pentadecanuclear cluster compounds: [Ni-II{Ni-II(MeOH)(3)}(8)(mu-CN)(30){M-V(CN)(3)}(6)].xMeOH.yH(2)O (M-V = Mo-V (1) with x = 17, y = 1; M-V = W-V (2) with x = 15, y = 0). Both compounds crystallize in the monoclinic space group C2/c, with cell dimensions of a = 28.4957(18) Angstrom, b = 19.2583(10) Angstrom, c = 32.4279(17) Angstrom, beta = 113.155(6)degrees, and Z = 4 for 1 and a = 28.5278(16) Angstrom, b = 19.2008(18) Angstrom, c = 32.4072(17) Angstrom, beta = 113.727(6)degrees, and Z = 4 for 2. The structures of 1 and 2 consist of neutral cluster complexes comprising 15 metal ions, 9 Ni-II and 6 M-V, all linked by mu-cyano ligands. Magnetic susceptibilities and magnetization measurements of compounds 1 and 2 in the crystalline and dissolved state indicate that these clusters have a S = 12 ground state, originating from intracluster ferromagnetic exchange interactions between the mu-cyano-bridged metal ions of the type Ni-II-NC-M-V. Indeed, these data show clearly that the cluster molecules stay intact in solution. Ac magnetic susceptibility measurements reveal that the cluster compounds exhibit magnetic susceptibility relaxation phenomena at low temperatures since, with nonzero dc fields, chi"M has a nonzero value that is frequency dependent. However, there appears no out-of-phase (chi"M) signal in zero dc field down to 1.8 K, which excludes the expected signature for a single molecule magnet. This finding is confirmed with the small uniaxial magnetic anisotropy value for D of 0.015 cm(-1), deduced from the high-field, high-frequency EPR measurement, which distinctly reveals a positive sign in D. Obviously, the overall magnetic anisotropy of the compounds is too low, and this may be a consequence of a small single ion magnetic anisotropy combined with the highly symmetric arrangement of the metal ions in the cluster molecule.