Realization of Organocerium-Based Fullerene Molecular Materials Showing Mott Insulator-Type Behavior

Electron-rich organocerium complexes (C 5 Me 4 H) 3 Ce and [(C 5 Me 5 ) 2 Ce( ortho -oxa)], with redox potentials E 1/2 = −0.82 V and E 1/2 = −0.86 V versus Fc/Fc +, respectively, were reacted with fullerene (C 60 ) in different stoichiometries to obtain molecular materials. Structurally characterized cocrystals: [(C 5 Me 4 H) 3 Ce] 2 ·C 60 ( 1 ) and [(C 5 Me 5 ) 2 Ce( ortho -oxa)] 3 ·C 60 ( 2 ) of C 60 with cerium-based, molecular rare earth precursors are reported for the first time. The extent of charge transfer in 1 and 2 was evaluated using a series of physical measurements: FT-IR, Raman, solid-state UV–vis–NIR spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and magnetic susceptibility measurements. The physical measurements indicate that 1 and 2 comprise the cerium(III) oxidation state, with formally neutral C 60 as a cocrystal in both cases. Pressure-dependent periodic density functional theory calculations were performed to study the electronic structure of 1 . Inclusion of a Hubbard-U parameter removes Ce f states from the Fermi level, opens up a band gap, and stabilizes FM/AFM magnetic solutions that are isoenergetic because of the large distances between the Ce(III) cations. The electronic structure of this strongly correlated Mott insulator-type system is reminiscent of the well-studied Ce 2 O 3 .