Interfacial magnetism in a fused superatomic cluster [Co6Se8(PEt3)5]2.

Abstract

An isolated Co6Se8(PEt3)6 cluster is non-magnetic; however, we find that a magnetic unit can be formed by fusing two Co6Se8(PEt3)5 superatoms into a [Co6Se8(PEt3)5]2 dimer. Theoretical studies indicate that the dumbbell-shaped [Co6Se8(PEt3)5]2 dimer has a spin moment of 2μB, and the spin density is primarily localized at the interfacial Co-sites where two clusters are fused into a dimer. The dimer has a low ionization energy of 4.17 eV, allowing the dimer to donate charge to C70 during the formation of a cluster assembled material, as seen in recent experiments by Nuckolls and co-workers. The donation of charge causes the dimer s magnetic moment to drop from 2μB to 1μB. We hypothesize that adding electrons to the dimer, such as doping impurities to the crystal lattice, may enhance the magnetic moment by neutralizing the charged cluster. This reveals a strategy for stabilizing magnetic moments in ligated cluster assemblies.