Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite

Abstract

The thermosalient effect is an extremely rare propensity of certain crystalline solids for self-actuation by elastic deformation or by a ballistic event. Here we present direct evidence for the driving force behind this impressive crystal motility. Crystals of a prototypical thermosalient material, (phenylazophenyl)palladium hexafluoroacetylacetonate, can switch between five crystal structures (α-ε) that are related by four phase transitions including one thermosalient transition (α↔γ). The mechanical effect is driven by a uniaxial negative expansion that is compensated by unusually large positive axial expansion (260 × 10(-6) K(-1)) with volumetric expansion coefficients (≈250 × 10(-6) K(-1)) that are among the highest values reported in molecular solids thus far. The habit plane advances at ~10(4) times the rate observed with non-thermosalient transitions. This rapid expansion of the crystal following the phase switching is the driving force for occurrence of the thermosalient effect.