Zero-field splitting (ZFS) of three high-spin Co(I) ( S = 1) clathrochelate complexes was determined by frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). The following axial and rhombic ZFS values ( D and E, respectively) were determined: [N( n-Bu)]Co(GmCl)(BPh) (1, D/ hc = +16.43(1) cm, E/ hc = 0.0(1) cm), [P(MeN)]Co(GmCl)(BPh) (2, D/ hc = +16.67(4) cm, E/ hc = 0.0(1) cm), and [P(CH)]Co(GmCl)(BPh) (3, D/ hc = +16.72(2) cm, E/ hc = 0.24(3) cm). Complementary susceptibility χ T measurements and quantum chemistry calculations on 1 revealed hard-axis-type magnetic anisotropy and allowed for a correlation of ZFS and the electronic structure. Increased rhombicity of 3 as compared to 1 and 2 was assigned to symmetry changes of the ligand structure induced by the change of the counterion. 1 and 3 exhibited temperature-dependent ZFS values. Possible reasons for this phenomenon, such as structural changes and weak chain-like intermolecular antiferromagnetic interactions, are discussed.
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