Paramagnetic anisotropy of planar cobalt(II) and copper(II) phthalocyanine, bis(pentane-2,4-dionato)copper(II), and bis(pentane-2,4-dithionato)cobalt(II)
- 1 January 1976
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 15,p. 1458-1466
- https://doi.org/10.1039/dt9760001458
Abstract
The principal crystalline and molecular susceptibilities, and their orientations, of cobalt(II) phthalocyanine, [Co(pc)], bis(pentane-2,4-dithionato)cobalt(II). [Co(pdt)2]. copper(II) phthalocyanine, [Cu(pc)], and bis-(pentane-2,4-dionato)copper(II), [Cu(pd)2], are reported. The diamagnetic anisotropy of the two pc derivatives makes a significant contribution to the observed anisotropy, especially in the cooper compound. The resulting paramagnetic anisotropy {and e.s.r. data in the case of [Co(pdt)2]} is then used to confirm the S=½ ground state of each compound [⋯ dz21 in both the cobalt(II) derivatives and dxy 1 in both the copper(II) derivatives]. The marked in-plane anisotropy in [Co(pdt)2], compared with the in-plane isotropy of [Co(pc)], is shown to arise from both the abnormally large splitting of the dxz, dyz pair of orbitals and the mixing of the dxy and dz 2 orbitals in low symmetry. An unambiguous assignment of two of the excited states in [Cu(pc)] can be made but ambiguities remain in [Cu(pd)2].Keywords
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