Metallization of a Hypervalent Radical Dimer: Molecular and Band Perspectives

Variable pressure and temperature conductivity measurements on the bisthiaselenazolyl radical dimer [1a]2 have established the presence of a weakly metallic state over the pressure range 5−9 GPa. To explore the origin of this metallization we have examined the crystal and molecular structure of [1a]2 as a function of pressure. At ambient pressure the dimer consists of two radicals linked by a hypervalent 4-center 6-electron S···Se−Se···S σ-bond into an essentially coplanar arrangement. The dimers are packed in cross-braced slipped π-stack arrays running along the x-direction of the monoclinic (space group P21/c) unit cell. Pressurization to 4 GPa induces little change in the molecular structure of [1a]2 or in the slipped π-stack crystal architecture. Near 5 GPa, however, stress on the dimer leads to buckling of the two halves of the molecule and a contraction in the metrics of the S···Se−Se···S unit. These structural changes can be understood in terms of an electronic configurational switch from a 4-center 6-electron σ-bonded dimer to a more conventional π-bonded arrangement. At the same time the slipped π-stack arrays undergo a concertina-like compression, and the crystal structure experiences highly anisotropic changes in cell dimensions. DFT calculations on the molecular electronic structure of the dimer indicate a marked decrease in the HOMO−LUMO gap as the dimer buckles. Related solid-state calculations indicate a rapid closure of the valence/conduction band gap in the same pressure region and the formation of a quasi-metallic state. Metallization of [1a]2 thus arises as much from intramolecular changes, which give rise to a collapse of the HOMO−LUMO gap and near coalescence of the valence and conduction bands, as from increased intermolecular interactions, which cause widening and overlap of the band edges.