Solid refrigerants exhibiting a caloric effect upon applying external stimuli are receiving attention as one of the next-generation refrigeration technologies. Herein, we report a new inorganic refrigerant, rubidium cyano-bridged manganese–iron–cobalt ternary metal assembly (cyano-RbMnFeCo). Cyano-RbMnFeCo shows a reversible barocaloric effect with large reversible adiabatic temperature changes of 74 K (from 57 °C to −17 °C) at 340 MPa, and 85 K (from 88 °C to 3 °C) at 560 MPa. Such large reversible adiabatic temperature changes have yet to be reported among caloric effects in solid–solid phase transition refrigerants. The reversible refrigerant capacity is 26000 J kg⁻¹ and the temperature window is 142 K. Additionally, cyano-RbMnFeCo shows barocaloric effects even at low pressures, e.g., reversible adiabatic temperature change is 21 K at 90 MPa. Furthermore, direct measurement of the temperature change using a thermocouple shows +44 K by applying pressure. The temperature increase and decrease upon pressure application and release are repeated over 100 cycles without any degradation of the performance. This material series also possesses a high thermal conductivity value of 20.4 W m⁻¹ K⁻¹. The present barocaloric material may realize a high-efficiency solid refrigerant.

Self-assembly of β-diketonate (Htta = thenoyl(trifluoro)acetone) and 4,4′-azopyridine (Azo-py) with neodymium(III) ions in the presence of methanol resulted in the formation of mononuclear complex [Nd^III(TTA)₃(MeOH)₂]·0.5Azo-py (A) in which two asymmetric units are linked by Azo-py through hydrogen bonding via methanol. A reveals near-infrared emission (NIR) centred at about 895 and 1056 nm, in the 10–370 K temperature range, originating from the two emissive transitions on Nd(III) from ⁴F_3/2 to ⁴I_9/2 and ⁴I_11/2 levels, respectively. Furthermore, the NIR luminescence intensity of A at room temperature augments two times upon thermal elimination of one coordinated methanol molecule. The thermally activated A exhibits single centre ratiometric thermometer behaviour in a wide temperature range from 10 to 300 K. Moreover, fluorescence properties of A were compared to another mononuclear complex [Nd^III(TTA)₃(4-OHpy)(H₂O)] (B). Assembly A also exhibits field-induced slow magnetic relaxation properties with an energy barrier of ΔE/k_B = 19.7(7) K and an attempt time of relaxation, τ₀ = 3.7(8) × 10⁻⁷ s for fresh sample A, and ΔE/k_B = 27.3 K and τ₀ = 8.5(0) × 10⁻⁸ for assembly A after thermal treatment at 370 K.