This
study probes the structure and magnetocaloric effect of the LnOHCO3 (Ln = Gd3+, Tb3+, Dy3+,
Ho3+, and Er3+) frameworks. The combination
of single crystal X-ray and neutron powder diffraction indicates that
these materials solely adopt the P212121 structure under these synthetic conditions and
magnetic susceptibility measurements indicate they remain paramagnetic
down to 2 K. We show that the magnetocaloric effects of TbOHCO3 and DyOHCO3 have peak entropy changes of 30.99
and 33.34 J kg–1 K–1 for a 2–0
T field change, respectively, which are higher than that of the promising
GdOHCO3 framework above 4 K in moderate magnetic fields.
The magnetic entropy changes of TbOHCO3 and DyOHCO3 above 4 K for smaller than 2 T field changes also exceed
those of Gd3Ga5O12 and Dy3Ga5O12, making them suitable magnetic cooling
materials for use at liquid helium temperatures using the low applied
magnetic fields accessible using permanent magnets, advantageous for
efficient practical cooling devices.
Barocaloric effects in a layered hybrid organic-inorganic compound, (C 10 H 21 NH 3 ) 2 MnCl 4 , that are reversible and colossal under pressure changes below 0.1 GPa are reported. This barocaloric performance originates in a phase transition characterized by different features: A strong disordering of the organic chains, a very large volume change, a very large sensitivity of the transition temperature to pressure and a small hysteresis. The obtained values are unprecedented among solid-state cooling materials at such low pressure changes and demonstrate that colossal effects can be obtained in compounds other than plastic crystals. The temperature-pressure phase diagram displays a triple point indicating enantiotropy at high pressure.
Magnetic materials with strong local interactions but lacking long-range order have long been a curiosity of physicists. Probing their magnetic interactions is crucial for understanding the unique properties they can exhibit. Metal-organic frameworks have recently gathered more attention as they can produce more exotic structures, allowing for controlled design of magnetic properties not found in conventional metal-oxide materials. Historically, magnetic diffuse scattering in such materials has been overlooked but has attracted greater attention recently, with advances in techniques. In this study, we investigate the magnetic structure of metal-organic formate frameworks, using heat capacity, magnetic susceptibility and neutron diffraction. In Tb(DCO
2
)
3
, we observe emergent magnetic order at temperatures below 1.2 K, consisting of two
k
-vectors. Ho(DCO
2
)
3
shows diffuse scattering above 1.6 K, consistent with ferromagnetic chains packed in a frustrated antiferromagnetic triangular lattice, also observed in Tb(DCO
2
)
3
above 1.2 K. The other lanthanides show no short- or long-range order down to 1.6 K. The results suggest an Ising-like one-dimensional magnetic order associated with frustration is responsible for the magnetocaloric properties, of some members in this family, improving at higher temperatures.
This article is part of the theme issue ‘Mineralomimesis: natural and synthetic frameworks in science and technology’.
Understanding how to tune magnetic interactions to optimise the magnetocaloric effect is crucial for designing more efficient solid state refrigerants; this work probes this relationship for the promising LnODCO3 phases.
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