Kerwyn G. Alley, Roland Bircher, Oliver Waldmann, Stefan T. Ochsenbein, Hans U. Güdel, Boujemaa Moubaraki, Keith S. Murray, Felix Fernandez-Alonso, Brendan F. Abrahams and Colette Boskovic
Mixed-Valent Cobalt Spin Clusters: a Hexanuclear Complex and a One-Dimensional Coordination Polymer Comprised of Alternating Hepta- and Mononuclear Fragments
Inorg. Chem. 45, 8950-8957 (2006)                             

Abstract: Reactions between Co(OAc)₂ and 2-amino-2-methyl-1,3-propanediol (ampdH₂) afford a hexanuclear complex [Co₆(H₂O)(MeOH)(OAc)₆(ampd)₄] (1) and a one-dimensional coordination polymer comprised of discrete heptanuclear complexes covalently bound to mononuclear Co centers [Co₈(H₂O)₂(OAc)₇(ampd)₆]_n (2). While 1 is obtained under ambient reaction conditions, the formation of 2 requires solvothermal methods. Both products have been characterized crystallographically and found to be mixed-valent, containing divalent and trivalent Co centers. Down to 30 K, the variable-temperature magnetic susceptibility data of 1 and 2 are dominated by the single-ion properties of high-spin Co^II centers with distorted-octahedral coordination geometries. Below this temperature, the effect of intramolecular ferromagnetic exchange interactions becomes apparent. The ferromagnetic coupling in 1 has been analyzed in terms of an anisotropic exchange model, and inelastic neutron scattering data are consistent with the proposed model. Although the structure of 2 precludes a quantitative interpretation, the magnetic data suggest ferromagnetic exchange within the heptanuclear unit and negligible interactions along the chain between the hepta- and mononuclear fragments.