Generalized Synthesis of Calixarene-Based High-Nuclearity M4n Nanocages (M = Ni or Co; n = 2鈥?)

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• 作者：Kongzhao Su ; Feilong Jiang ; Jinjie Qian ; Yanli Gai ; Mingyan Wu ; Salem M. Bawaked ; Mohamed Mokhtar ; Shaeel A. AL-Thabaiti ; Maochun Hong
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：June 4, 2014
• 年：2014
• 卷：14
• 期：6
• 页码：3116-3123
• 全文大小：468K
• 年卷期：v.14,no.6(June 4, 2014)
• ISSN：1528-7505

文摘

A family of high-nuclearity M<sub>4nsub> (M = Ni or Co, n = 2鈥?) coordination nanocages constructed by M<sub>4sub>鈥揷alix[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>4sub>鈥揷alix[4]arene MBBs, including Ni<sub>8sub> (1 and 2, n = 2), M<sub>12sub> (M = Ni (3) and Co (4), n = 3), M<sub>16sub> (M = Ni (5) and Co (6), n = 4), Co<sub>20sub> (7, n = 5), and Co<sub>24sub> (8, n = 6) coordination nanocages. Structural analyses reveal that the metallic cores of 1 and 2 are arranged in chair conformation, while compounds 3鈥?b>6 with closed-shell structures, where their ports are sealed by sodium ions, present the first examples of 2p-3d heterometallic metal鈥揷alixarene nanocages to our knowledge. The novel helmet-like Co<sub>20sub> (7) is the only one in this family with an open-shell structure, which can be thought of as a truncated octahedral Co<sub>24sub> (8) nanocage cutting one face. Furthermore, the magnetic behaviors of 1鈥?b>8 have been investigated, suggesting the existence of strong antiferromagnetic interactions between magnetic centers for all title coordination cages.