期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 31, 页码 7906-7912出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201800516
关键词
cluster compounds; cobalt; density functional calculations; mass spectrometry; self-assembly
资金
- National Science Foundation for Distinguished Young Scholars of China [21525101]
- NSF of China, Hubei and Guangxi Province [91422302, 2017CFA006, 2014GXNSFFA118003, 2017GXNSFDA198040]
- BAGUI scholar program [2014A001]
- Project of Talents Highland of Guangxi Province
- CNRS of France
Two heptanuclear discs, [Co-7(L1)(6)(CH3O)(6)](2+) (Co-7-L1) and [Co-7(L2)(12)](ClO4)(2) (Co-7-L2), have been prepared by the reaction of [Co(H2O)(6)](CIO4)(2) with Schiff base HL1 (HL1=2-methoxy-6-[(methylimino)methyl]phenolate) or benzimidazole derivative HL2 (HL2=(1H-benzo[d]imidazol-2-yl)methanolate), respectively, at room temperature. In contrast, the reaction of [Co(H2O)(6)](CIO4)(2) with a mixture of the two ligands, having similar coordination ability but different shapes, resulted in the butterfly-structured tetranuclear cobalt cluster [Co-4(L1)(2)(L2)(4)](CIO4)(2)2H(2)O (Co-4). Electrospray ionization mass spectrometry (ESI-MS) analysis in real time revealed the {Co-1}->{Co-2}->{Co-4}->{Co-7} stepwise assembly when a single ligand was employed, but when both ligands were used only {Co-4} was obtained, an intermediate of the former reactions. Interestingly, ligand competition was evidenced in the assembly process of the reaction with two ligands; for example, [Co-4(L1)(4)(L2)(2)](2+) and [Co-4(L1)(3)(L2)(3)](2+) were the primary clusters observed at the beginning of the reaction, but [Co-4(L1)(2)(L2)(4)](2+) was the final product. This observation suggests ligand exchange is taking place, and DFT calculations confirmed that these transformations were possible. By varying the ratio of ligands, the abundance of a certain species in the competitive reaction could be controlled.
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