Radical anion salt {cryptand[2.2.2] (K+ )}2 (bispheroid)2- ⋅3.5C6 H4 Cl2 (1) of the double-caged fullerene C60 derivative, in which fullerene cages are linked by a cyclobutane bridging cycle and additionally by a pyrrolizidine moiety, was obtained. Each fullerene cage in this derivative accepts one electron on reduction, thus forming the (bispheroid)2- dianions with two interacting S=1/2 spins on the neighboring cages. Low-temperature magnetic measurements reveal a singlet ground state of the bispheroid dianions whereas triplet contributions prevail at increased temperature. An estimated exchange interaction between two spins J/kB =-78 K in 1 indicates strong magnetic coupling between them, nearly two times higher than that (J/kB =-44.7 K) in previously studied (C60 - )2 dimers linked via a cyclobutane bridge only. The enhancement of magnetic coupling in 1 can be explained by a shorter distance between the fullerene cages and, possibly, an additional channel for the magnetic exchange provided by a pyrrolizidine bridge. Quantum-chemical calculations of the lowest electronic state of the dianions by means of multi-configuration quasi-degenerate perturbation theory support the experimental findings.
Keywords: DFT calculations; crystal structure; fullerene C60 derivatives; optical and magnetic properties; reduction; singlet-triplet transitions.
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