Neodymium β-diketonate showing slow magnetic relaxation and acting as a ratiometric thermometer based on near-infrared emission

Abstract

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.