Syntheses, Crystal Structures, and Magnetic Properties of Two <i>p</i>-<i>tert</i>-Butylsulfonylcalix[4]arene Supported Cluster Complexes with a Totally Disordered Ln₄(OH)₄ Cubane Core

Two new sandwich calix[4]­arene-supported cluster complexes, [Ln4(OH)4­(TBSOC)2­(H2O)4­(CH3OH)4]­·4H2O (H4TBSOC = p-tert-butylsulfonylcalix­[4]­arene; Ln = Dy, 1; Ln = Ho, 2), have been prepared and characterized. An X-ray crystallographic study reveals that both complexes contain a holistically disordered [Ln4(OH)4]8+ cubane cluster core, which is sandwiched between two antiparallel calixarene macrocycles. Magnetic investigations indicate that complex 1 displays slow magnetization relaxation typical for single-molecule magnets in the absence of a static applied dc field, with the ΔE/kB parameter of 22.9 K, the largest value for the calixarene-supported pure 4f single-molecule magnets so far, whereas complex 2 does not show any relaxation of the magnetization above 2 K.本研究合成并表征了两种新型三明治型杯[4]芳烃负载簇合物：[Ln4(OH)4(TBSOC)2(H2O)4(CH3OH)4]·4H2O（其中H4TBSOC = 对叔丁基磺酰基杯[4]芳烃(p-tert-butylsulfonylcalix[4]arene)，Ln分别为镝（对应化合物1）、钬（对应化合物2)）。X射线晶体学研究结果显示，两种配合物均含有整体无序的[Ln4(OH)4]8+立方烷簇核，该簇核夹于两个反平行排布的杯芳烃大环之间。磁性表征结果表明，在未施加外加静态直流磁场的条件下，化合物1展现出单分子磁体（Single-Molecule Magnets）典型的慢磁化弛豫行为，其ΔE/kB参数为22.9 K，这是目前已报道的杯芳烃负载型纯4f区单分子磁体中的最高值；而化合物2在2 K以上的温度区间内未表现出任何磁化弛豫现象。