Abstract
AbstractThe synthesis and characterization of a family of compounds (pipzH2)[CrIII2LnIII4(µ4‐O)2(µ3‐OH)4(H2O)10(µ3‐SO4)4(SO4)2]·2H2O [hereafter abbreviated as Cr2Ln4; Ln = Tb (1), Ho (2), Er (3), Yb (4), and Y (5); pipz = piperazine] are reported. The compounds were obtained from hydrothermal reactions of Ln(NO3)3·6H2O (Ln = Tb, Ho, Er, Yb, and Y), Cr(NO3)3·9H2O, Na2SO4, and pipz in a 2:1:3:4 molar ratio. Single‐crystal X‐ray diffraction studies revealed that 1–5 crystallize isomorphously in the space group P21/c with Z = 2. The metallic core is composed of a rare face‐fused double‐cubane [CrIII2LnIII4(µ4‐O2–)2(µ3‐OH–)4]10+ unit. The temperature dependence of bulk magnetic susceptibilities is indicative of antiferromagnetic interactions dominant in the Tb, Ho, and Er compounds. In fitting with the data of the diamagnetic YIII analogue, the interactions of Cr–Cr in this system are determined to be ferromagnetic with a coupling strength of 3.61(11) cm–1, but the type of Cr–Ln could be antiferromagnetic. The dynamic magnetic properties revealed the presence of slow magnetic relaxation in the Tb and Er analogues, which represent two rare examples of CrIII‐containing clusters that exhibit single‐molecule magnet (SMM) behavior.
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