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

Thiacalix[4]arenes\nare a class of macrocyclic ligands employed\nto assemble high-nuclear-weight clusters, yet deciphering their structure\nand assembly process at the atomic level continues to pose a formidable\nchallenge. Here, we report four bowl-shaped high-nuclearity 3d–4f\nclusters, {GdNi<sub>12</sub>[TC4A]<sub>3</sub>[CO<sub>3</sub>]<sub>3</sub>[HCOO]<sub>6</sub>[OCH<sub>3</sub>]<sub>3</sub>}·20H<sub>2</sub>O ({<b>GdNi</b><sub><b>12</b></sub><b>})</b>, {Gd<sub>2</sub>Ni<sub>28</sub>[TC4A]<sub>6</sub>[CO<sub>3</sub>]<sub>8</sub>[HCOO]<sub>10</sub>[OCH<sub>3</sub>]<sub>4</sub>[μ<sub>3</sub>–OH]<sub>6</sub>[μ<sub>2</sub>–OH]<sub>2</sub>}·17H<sub>2</sub>O ({<b>Gd</b><sub><b>2</b></sub><b>Ni</b><sub><b>28</b></sub><b>}</b>), {Gd<sub>4</sub>Ni<sub>24</sub>[TC4A]<sub>6</sub>[CO<sub>3</sub>]<sub>6</sub>[HCOO]<sub>16</sub>[OCH<sub>3</sub>]<sub>8</sub>[μ<sub>3</sub>–OH]<sub>6</sub>}·10H<sub>2</sub>O ({<b>Gd</b><sub><b>4</b></sub><b>Ni</b><sub><b>24</b></sub><b>}</b>), and {Gd<sub>5</sub>Ni<sub>26</sub>[TC4A]<sub>6</sub>[MA]<sub>2</sub>[CO<sub>3</sub>]<sub>6</sub>[HCOO]<sub>6</sub>[OCH<sub>3</sub>]<sub>4</sub>[μ<sub>3</sub>–OH]<sub>10</sub>}·5H<sub>2</sub>O ({<b>Gd</b><sub><b>5</b></sub><b>Ni</b><sub><b>26</b></sub><b>}</b>) (H<sub>2</sub>MA = malicacid),\nprotected by the <i>p</i>-<i>tert</i>-butylthiacalix[4]arene\n(H<sub>4</sub>TC4A) ligand. The <b>{GdNi</b><sub><b>12</b></sub><b>}</b> cluster has a bowl-shaped architecture composed\nof the [NiO<sub>6</sub>], [GdO<sub>10</sub>], and [CO<sub>3</sub>]\ngroups. Meanwhile, <b>{Gd</b><sub><b>2</b></sub><b>Ni</b><sub><b>28</b></sub><b>}</b>, <b>{Gd</b><sub><b>4</b></sub><b>Ni</b><sub><b>24</b></sub><b>}</b>, and <b>{Gd</b><sub><b>5</b></sub><b>Ni</b><sub><b>26</b></sub><b>}</b> present a mouth-to-mouth\nskew-symmetric bowl-shaped structure, each composed of <b>{GdNi</b><sub><b>12</b></sub><b>}</b> cluster units. Magnetic\nstudies revealed ferromagnetic interactions within <b>{GdNi</b><sub><b>12</b></sub><b>}</b> and <b>{Gd</b><sub><b>2</b></sub><b>Ni</b><sub><b>28</b></sub><b>}</b> clusters. This work not only reveals the effect of macrocyclic\nligands on the formation of high-nuclearity 3d–4f clusters\nbut also provides a new structural prototype to understand their assembly\nrules.