Lanthanide-radical magnetic coupling in [LnPc$_2$]$^0$: Competing exchange mechanisms captured via ab initio multi-reference calculations

We present a computational investigation of the intramolecular exchange coupling in [LnPc$_2$]$^0$ (Ln = Tb, Dy, Ho, and Er) between the Ln$^{3+}$ 4f electrons and the spin-1/2 radical on the phthalocyanine ligands. A series of ab initio multi-configurational/multi-reference Complete/Restricted Active Space Self-Consistent-Field calculations (CASSCF/RASSCF), including non-perturbative spin--orbit coupling, were performed on [LnPc$_2$]$^0$ and on the smaller model compound [LnPz$_2$]$^0$. We find that the exchange coupling mechanisms are restricted by symmetry, but also dependent on the spin polarization effect triggered by the Pc$_2$ ligands $π$--$π^*$ excitations. The calculated exchange splittings are small, amounting to at most a few cm$^{-1}$, in disagreement with previous literature reports of strong antiferromagnetic coupling, but in good agreement with recent EPR experiments on [TbPc$_2$]$^0$. Furthermore, the coupling strength is found to decrease from [TbPc$_2$]$^0$ to [ErPc$_2$]$^0$, with decreasing number of unpaired electron spins in the lanthanide ground (Hund's rule) Russell--Saunders term.

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