Pancakes under Pressure: A Case Study on Isostructural Dithia- and Diselenadiazolyl Radical Dimers

The isostructural dimers of the 1,4-phenylene-bridged bis-1,2,3,5-dithia- and bis-1,2,3,5-diselenadiazolyl diradicals 1,4-S/Se are small band gap semiconductors. The response of their molecular and solid state electronic structures to pressure has been explored over the range 0-10 GPa. The crystal structures, which consist of cofacially aligned (pancake) π-dimers packed into herringbone arrays, experience a continuous, near-isotropic compression. While the intramolecular covalent E-E (E = S/Se) bonds remain relatively unchanged with pressurization, the intradimer E···E separations are significantly shortened. Molecular and band electronic structure calculations using density functional theory methods indicate that compression of the π-dimers leads to a widening of the gap Δ E between the highest occupied and lowest unoccupied molecular orbitals of the dimer, an effect that offsets the expected decrease in the valence-to-conduction band gap E