From Magnets to Metals: The Response of Tetragonal Bisdiselenazolyl Radicals to Pressure

The bromo-substituted bisdiselenazolyl radical 4b (R1 = Et, R2 = Br) is isostructural with the corresponding chloro-derivative 4a (R1 = Et, R2 = Cl), both belonging to the tetragonal space group P421m and consisting of slipped π-stack arrays of undimerized radicals. Variable temperature, ambient pressure conductivity measurements indicate a similar room temperature conductivity near 10−4 S cm−1 for the two compounds, but 4b displays a slightly higher thermal activation energy Eact (0.23 eV) than 4a (0.19 eV). Like 4a, radical 4b behaves as a bulk ferromagnet with an ordering temperature of TC = 17.5 K. The coercive field Hc (at 2 K) of 1600 Oe for 4b is, however, significantly greater than that observed for 4a (1370 Oe). High pressure (0−15 GPa) structural studies on both compounds have shown that compression reduces the degree of slippage of the π-stacks, which gives rise to changes in the magnetic and conductive properties of the radicals. Relatively mild loadings (<2 GPa) cause an increase in TC for b...