10.1021/cg5003836.s002 Kongzhao Su Kongzhao Su Feilong Jiang Feilong Jiang Jinjie Qian Jinjie Qian Yanli Gai Yanli Gai Mingyan Wu Mingyan Wu Salem M. Bawaked Salem M. Bawaked Mohamed Mokhtar Mohamed Mokhtar Shaeel A. AL-Thabaiti Shaeel A. AL-Thabaiti Maochun Hong Maochun Hong Generalized Synthesis of Calixarene-Based High-Nuclearity M<sub>4<i>n</i></sub> Nanocages (M = Ni or Co; <i>n</i> = 2–6) American Chemical Society 2014 chair conformation antiferromagnetic interactions Ni building blocks sodium ions title coordination cages Generalized Synthesis Co Structural analyses solvothermal syntheses MBB phosphonate ligands nanocage 2014-06-04 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Generalized_Synthesis_of_Calixarene_Based_High_Nuclearity_M_sub_4_i_n_i_sub_Nanocages_M_Ni_or_Co_i_n_i_2_6_/2286532 A family of high-nuclearity M<sub>4<i>n</i></sub> (M = Ni or Co, <i>n</i> = 2–6) coordination nanocages constructed by M<sub>4</sub>–calix­[4]­arene molecular building blocks (MBBs) with inorganic phosphate or organic phosphonate ligands have been isolated by solvothermal syntheses and characterized by single-crystal X-ray diffraction. This family can be divided into five structural types with an increase in the number of M<sub>4</sub>–calix­[4]­arene MBBs, including Ni<sub>8</sub> (<b>1</b> and <b>2</b>, <i>n</i> = 2), M<sub>12</sub> (M = Ni (<b>3</b>) and Co (<b>4</b>), <i>n</i> = 3), M<sub>16</sub> (M = Ni (<b>5</b>) and Co (<b>6</b>), <i>n</i> = 4), Co<sub>20</sub> (<b>7</b>, <i>n</i> = 5), and Co<sub>24</sub> (<b>8</b>, <i>n</i> = 6) coordination nanocages. Structural analyses reveal that the metallic cores of <b>1</b> and <b>2</b> are arranged in chair conformation, while compounds <b>3</b>–<b>6</b> with closed-shell structures, where their ports are sealed by sodium ions, present the first examples of 2p-3d heterometallic metal–calixarene nanocages to our knowledge. The novel helmet-like Co<sub>20</sub> (<b>7</b>) is the only one in this family with an open-shell structure, which can be thought of as a truncated octahedral Co<sub>24</sub> (<b>8</b>) nanocage cutting one face. Furthermore, the magnetic behaviors of <b>1</b>–<b>8</b> have been investigated, suggesting the existence of strong antiferromagnetic interactions between magnetic centers for all title coordination cages.