Barocaloric effectsthermal
changes in a material induced
by applied hydrostatic pressureoffer promise for creating
solid-state refrigerants as alternatives to conventional volatile
refrigerants. To enable efficient and scalable barocaloric cooling,
materials that undergo high-entropy, reversible phase transitions
in the solid state in response to a small change in pressure are needed.
Here, we report that pressure-induced spin-crossover (SCO) transitions
in the molecular iron(II) complex Fe[HB(tz)3]2 (HB(tz)3
– = bis[hydrotris(1,2,4-triazol-1-yl)borate])
drive giant and reversible barocaloric effects at easily accessible
pressures. Specifically, high-pressure calorimetry and powder X-ray
diffraction studies reveal that pressure shifts as low as 10 bar reversibly
induce nonzero isothermal entropy changes, and a pressure shift of
150 bar reversibly induces a large isothermal entropy change (>90
J kg–1 K–1) and adiabatic temperature
change (>2 K). Moreover, we demonstrate that the thermodynamics
of
the SCO transition can be fine-tuned through systematic deuteration
of the tris(triazolyl)borate ligand. These results provide new insights
into pressure-induced SCO transitions and further establish SCO materials
as promising barocaloric materials.