Giant and Reversible Barocaloric Effect in Trinuclear Spin‐Crossover Complex Fe3(bntrz)6(tcnset)6
- 2 February 2021
- journal article
- research article
- Published by Wiley in Advanced Materials
- Vol. 33 (10), 2008076
- https://doi.org/10.1002/adma.202008076
Abstract
A giant barocaloric effect (BCE) in a molecular material Fe3(bntrz)6(tcnset)6 (FBT) is reported, where bntrz = 4‐(benzyl)‐1,2,4‐triazole and tcnset = 1,1,3,3‐tetracyano‐2‐thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin‐state switching between the state in which all three FeII centers are in the high‐spin (S = 2) electronic configuration and the state in which all of them are in the low‐spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X‐ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin‐transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg−1 K−1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far.Keywords
Funding Information
- Ministerio de Economía y Competitividad (MAT2016‐ 75823‐R, FIS2017‐82625‐P, FIS2017‐83295‐P)
- Deutsche Gesellschaft für Urologie (2017SGR‐42)
- National Science Foundation (CHE‐1955754, DMR‐1644779)
- U.S. Department of Energy
- Basic Energy Sciences (DE‐SC0002613)
- Türkiye Bilimsel ve Teknolojik Araştırma Kurumu (MFAG‐118F128)
- China Scholarship Council
- Florida State University (201706460046)
- National High Magnetic Field Laboratory
- Universitat de Barcelona
This publication has 48 references indexed in Scilit:
- Advanced materials for solid-state refrigerationJournal of Materials Chemistry A, 2013
- Inverse barocaloric effect in the giant magnetocaloric La–Fe–Si–Co compoundNature Communications, 2011
- Giant solid-state barocaloric effect in the Ni–Mn–In magnetic shape-memory alloyNature Materials, 2010
- Equations of state of MgO, Au, Pt, NaCl-B1, and NaCl-B2: Internally consistent high-temperature pressure scalesHigh Pressure Research, 2007
- The spin-states and spin-transitions of mononuclear iron(II) complexes of nitrogen-donor ligandsPolyhedron, 2007
- Properties of Prussian Blue Materials Manifested in Molecular Complexes: Observation of Cyanide Linkage Isomerism and Spin-Crossover Behavior in Pentanuclear Cyanide ClustersJournal of the American Chemical Society, 2007
- Pressure-Induced Colossal Magnetocaloric Effect in MnAsPhysical Review Letters, 2004
- Pressure Enhancement of the Giant Magnetocaloric Effect inPhysical Review Letters, 2004
- Itinerant-electron metamagnetism and strong pressure dependence of the Curie temperaturePhysical Review B, 2001
- Cooling by adiabatic pressure application in Pr1−xLaxNiO3Applied Physics Letters, 1998