期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 70, 期 5, 页码 1558-1564出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo047892w
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The encapsulation of cobaltocenium (Cob) inside hexameric molecular capsules of two different resorcinarenes was investigated in dichloromethane solution. Both H-1 NMR spectroscopic and voltammetric experiments clearly reveal that Cob(+) experiences encapsulation. Diffusion coefficient measurements obtained from PGSE NMR experiments indicate that the molecular capsules exist in dichloromethane solution in the absence of any cations. Bound and free Cob(+) ions undergo slow exchange on the NMR time scale, but the bound Cob(+) ions rotate and/or tumble freely inside the molecular capsules. Under experimental conditions suitable for voltammetry the encapsulation of Cob(+) depends on the nature of the supporting electrolyte. Tetraalkylammonium hexafluorophosphate, tetrafluoroborate, and perchlorate supporting electrolytes prevent the encapsulation of Cob(+), while tetraalkylammonium chloride and bromide salts allow it. The nature of the tetraalkylammonium cation plays a smaller role in the encapsulation. Finally, the structure of the resorcinarene also factors into the overall stability of the molecular assembly.
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