Analysis of the uniaxial magnetic properties of high-spin d(6) ions at trigonal prism and linear two-coordinate sites: uniaxial magnetic properties of Ca(3)Co(2)O(6) and Fe[C(SiMe(3))(3)](2).

It was shown that high-spin d(6) ions at trigonal prism and linear two coordinate sites have uniaxial magnetic properties by calculating their low-lying eigenstates under the influence of crystal field and spin-orbit coupling and then determining their g-factors for the parallel and perpendicular directions. On the basis of our theoretical findings, we interpreted the uniaxial magnetic properties of Ca(3)Co(2)O(6) with high-spin Co(3+) (d(6)) ions at the trigonal prism sites and those of FeC(SiMe(3))(3) with high-spin Fe(2+) (d(6)) ions at linear two-coordinate sites, and discussed why compounds with high-spin d(6) ions at octahedral sites cannot have uniaxial magnetic properties.