Publication | Open Access
Effect of linear and non-linear pseudohalides on the structural and magnetic properties of Co(<scp>ii</scp>) hexacoordinate single-molecule magnets
37
Citations
90
References
2017
Year
A series of mononuclear hexacoordinate Co(ii) complexes with the 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole (abpt) ligand and various linear and non-linear pseudohalides, such as NCSe (selenocyanate), N{C(CN)<sub>2</sub>}<sub>2</sub> (1,1,3,3-tetracyano-2-azapropenide, tcap), NO<sub>2</sub>C(CN)<sub>2</sub> (nitrodicyanomethanide, nodcm), C(CN){C(CN)<sub>2</sub>}<sub>2</sub> (1,1,2,3,3-pentacyanopropenide, pcp), NO<sub>2</sub>NCN (nitrocyanamide, nca), and ONC(CN)<sub>2</sub> (nitrosodicyanomethanide, ndcm), was prepared. X-ray analyses revealed the formation of the complexes with the general compositions [Co(abpt)<sub>2</sub>(solv)<sub>2</sub>]X<sub>2</sub> (solv = H<sub>2</sub>O and X = tcap (1), solv = H<sub>2</sub>O and X = nodcm (2), solv = CH<sub>3</sub>OH and X = pcp (3)) or [Co(abpt)<sub>2</sub>(X)<sub>2</sub>] (X = nca (4), X = NCSe (5), X = ndcm (6)). The impact of axial co-ligands (solv or X) on the magnetic properties was investigated experimentally by measuring temperature- and field-dependent static (DC) and dynamic magnetic (AC) data as well as theoretically using the CASSCF/NEVPT2, AILFT, and AOM methods. Large magnetic anisotropy was found for all complexes 1-6 and was treated either by the spin Hamiltonian or with the Hamiltonian including the orbital angular momentum. Furthermore, the AC susceptibility measurements confirmed the slow relaxation of the magnetization in a non-zero static magnetic field, thus these complexes can be classified as field-induced single-molecule magnets with an estimated energy barrier U<sub>eff</sub> up to 100 K.
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