Reversible and high-contrast thermal conductivity switching in a flexible covalent organic framework possessing negative Poisson's ratio†

The ability to dynamically and reversibly control thermal transport in solid-state systems can redefine and propel a plethora of technologies including thermal switches, diodes, and rectifiers. Current material systems, however, do not possess the swift and large changes in thermal conductivity required for such practical applications. For instance, stimuli responsive materials, that can reversibly switch between a high thermal conductivity state and a low thermal conductivity state, are mostly limited to thermal switching ratios in the range of 1.5 to 4. Here, we demonstrate reversible thermal conductivity switching with an unprecedented 18× change in thermal transport in a highly flexible covalent organic framework with revolving imine bonds. The pedal motion of the imine bonds is capable of reversible transformations of the framework from an expanded (low thermal conductivity) to a contracted (high thermal conductivity) phase, which can be triggered through external stimuli such as exposure to guest adsorption and desorption or mechanical strain. We also show that the dynamic imine linkages endow the material with a negative Poisson's ratio, thus marking a regime of materials design that combines low densities with exceptional thermal and mechanical properties.