On the controversial fitting of susceptibility curves of ferromagnetic Cu(II) cubanes: insights from theoretical calculations.

This paper reports a theoretical analysis of the electronic structure and magnetic properties of a tetranuclear Cu(II) complex, [Cu(4) (HL)(4)], which has a 4+2 cubane-like structure (H(3) L=N,N'-(2-hydroxypropane-1,3-diyl)bis(acetylacetoneimine)). These theoretical calculations indicate a quintet (S=2) ground state; the energy-level distribution of the magnetic states confirm Heisenberg behaviour and correspond to an S(4) spin-spin interaction model. The dominant interaction is the ferromagnetic coupling between the pseudo-dimeric units (J(1) =22.2 cm(-1)), whilst a weak and ferromagnetic interaction is found within the pseudo-dimeric units (J(2) =1.4 cm(-1)). The amplitude and sign of these interactions are consistent with the structure and arrangement of the magnetic Cu 3d orbitals; they accurately simulate the thermal dependence of magnetic susceptibility, but do not agree with the reported J values (J(1) =38.4 cm(-1), J(2) =-18.0 cm(-1)) that result from the experimental fitting. This result is not an isolated case; many other polynuclear systems, in particular 4+2 Cu(II) cubanes, have been reported in which the fitted magnetic terms are not consistent with the geometrical features of the system. In this context, theoretical evaluation can be considered as a valuable tool in the interpretation of the macroscopic behaviour, thus providing clues for a rational and directed design of new materials with specific properties.