Temperature-Induced Assembly of Thiacalix[4]arene-Protected Bowl-Shaped High-Nuclearity 3d-4f Clusters

Thiacalix[4]arenes are a class of macrocyclic ligands employed to assemble high-nuclear-weight clusters, yet deciphering their structure and assembly process at the atomic level continues to pose a formidable challenge. Here, we report four bowl-shaped high-nuclearity 3d-4f clusters, {GdNi12[TC4A]3[CO3]3[HCOO]6[OCH3]3}<middle dot>20H2O ({GdNi 12 }), {Gd2Ni28[TC4A]6[CO3]8[HCOO]10[OCH3]4[mu 3-OH]6[mu 2-OH]2}<middle dot>17H2O ({Gd 2 Ni 28 }), {Gd4Ni24[TC4A]6[CO3]6[HCOO]16[OCH3]8[mu 3-OH]6}<middle dot>10H2O ({Gd 4 Ni 24 }), and {Gd5Ni26[TC4A]6[MA]2[CO3]6[HCOO]6[OCH3]4[mu 3-OH]10}<middle dot>5H2O ({Gd 5 Ni 26 }) (H2MA = malicacid), protected by the p-tert-butylthiacalix[4]arene (H4TC4A) ligand. The {GdNi 12 } cluster has a bowl-shaped architecture composed of the [NiO6], [GdO10], and [CO3] groups. Meanwhile, {Gd 2 Ni 28 }, {Gd 4 Ni 24 }, and {Gd 5 Ni 26 } present a mouth-to-mouth skew-symmetric bowl-shaped structure, each composed of {GdNi 12 } cluster units. Magnetic studies revealed ferromagnetic interactions within {GdNi 12 } and {Gd 2 Ni 28 } clusters. This work not only reveals the effect of macrocyclic ligands on the formation of high-nuclearity 3d-4f clusters but also provides a new structural prototype to understand their assembly rules.