Slow magnetic relaxation of a S = 1/2 copper(II)-substituted Keggin-type silicotungstate

This is the first report on slow magnetic relaxation in an S = 1/2 system based on a first-row transition metal ion with the polyoxometalate skeleton [(n-C₄H₉)₄N]₄H₂[SiW₁₁O₃₉Cu] (1). The X-band electron-spin-resonance spectrum of 1 measured at room temperature indicates that the copper ion experiences significantly reduced intermolecular interactions compared to the potassium salt and that it adopts a five-coordinated square-pyramidal coordination geometry. The AC magnetic-susceptibility measurements revealed that 1 undergoes slow magnetic relaxation in an applied static magnetic field (H_dc). The extracted spin-lattice relaxation time (92 ms at 1.8 K and H_dc = 5000 Oe) for 5% magnetically diluted 1, [(n-C₄H₉)₄N]₄H₂[SiW₁₁O₃₉Cu_0.05Zn_0.95] (dil.1), is comparable to those of other potential S = 1/2 spin qubits. A relaxation-time analysis indicated that Raman spin-lattice relaxation dominates even at low temperatures in an optimized field. The extracted Raman exponent (n = 2.30) is smaller than those of other S = 1/2 complexes that carry organic ligands, which implies that the decrease in relaxation time at higher temperatures is likely to be moderate.