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Synthesis, Structure, and Magnetic Properties of Two {Co16IICo4III} Supertetrahedral T4 Clusters Formed from the In Situ Dissociation of a Tertiary N-Containing Ligand
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2023-03-02 , DOI: 10.1021/acs.cgd.3c00094
Mei-Yu Xu 1, 2 , Tong-Wei Zhang 2, 3 , Zhong-Mei Xian 1 , Jie Yang 1 , Zeng-Ni Xiang 1 , Ji-Lan Long 1 , Lei Xu 1 , Guang-Ming Liang 1, 2 , Peng Xiong 2 , Xiu-Jian Wang 2
Affiliation  

Two mixed-valent cobalt clusters {[(CoII)16(CoIII)46-O)43-OH)12(OCH3)12(H2O)8(BMBC)4]·(NO3)8} (1) and {[(CoII)16(CoIII)43-OH)20(OCH2CH3)4(HOCH2CH3)8(BMBC)4]·(NO3)8} (2) were synthesized and constructed by a semiflexible dicarboxylic ligand 4′,4′-[ammoniobis(methylene)]-bis[(1,1′-biphenyl)-2-carboxylate] (BMBC) with Co(NO3)2·6H2O under solvothermal systems. Interestingly, the ligand BMBC- is afforded from the in situ dissociation reaction of tertiary N-containing organic carboxylic acid ligands. The complexes present a beautiful supertetrahedral T4 cluster formed by an interior Co4IIIO4 cubane and four exterior Co4IIO4 cubanes bridged via μ6-O2 and μ3-OH ions and stabilized by four BMBC organic ligands. The complexes were confirmed by single-crystal X-ray diffraction (XRD), elemental analysis, infrared spectroscopy, and thermogravimetric analysis. Furthermore, the magnetic analyses reveal that the [Co20] cluster exhibits an antiferromagnetic behavior.

中文翻译:

由叔含氮配体原位解离形成的两个 {Co16IICo4III} 超四面体 T4 簇的合成、结构和磁性

两个混合价钴簇{[(Co II ) 16 (Co III ) 46 -O) 43 -OH) 12 (OCH 3 ) 12 (H 2 O) 8 (BMBC) 4 ]·( NO 3 ) 8 } (1) 和 {[(Co II ) 16 (Co III ) 43 -OH) 20 (OCH 2 CH 3 ) 4 (HOCH 2 CH 3 ) 8(BMBC) 4 ]·(NO 3 ) 8 } (2) 由半柔性二羧酸配体4',4'-[氨双(亚甲基)]-双[(1,1'-联苯)-2-合成构建carboxylate] (BMBC ) with Co(NO 3 ) 2 ·6H 2 O 在溶剂热系统下。有趣的是,配体 BMBC -是由含叔 N 的有机羧酸配体的原位解离反应提供的。这些配合物呈现出美丽的超四面体 T 4星团,由一个内部 Co 4 III O 4立方烷和四个外部 Co 4 II O组成4 个立方烷通过μ 6 - O 2和 μ 3 -OH -离子桥接,并由四个 BMBC -有机配体稳定。通过单晶 X 射线衍射 (XRD)、元素分析、红外光谱和热重分析证实了配合物。此外,磁性分析表明 [Co 20 ] 簇表现出反铁磁行为。
更新日期:2023-03-02
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