Syntheses, Structures, and Electrochemical Properties of Inclusion Compounds of Cucurbit[8]uril with Cobalt(III) and Nickel(II) Complexes

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• 作者：Tatiana V. Mitkina ; Nina F. Zakharchuk ; Dmitry Y. Naumov ; Olga A. Gerasko ; Dieter Fenske ; Vladimir P. Fedin
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：August 4, 2008
• 年：2008
• 卷：47
• 期：15
• 页码：6748-6755
• 全文大小：310K
• 年卷期：v.47,no.15(August 4, 2008)
• ISSN：1520-510X

文摘

Inclusion compounds of a macrocyclic cavitand cucurbit[8]uril (CB[8]) with cobalt(III) and nickel(II) complexes of 1,3-diaminopropane (tn) and 1,3-diamino-2-propanol (tmOH) {trans-[Co(tn)₂Cl₂]@CB[8]}Cl·14H₂O (1), {trans-[Co(tmOH)(tmO)]@CB[8]}Cl₂·22H₂O (2), and {trans-[Ni(tmOH)₂]@CB[8]}Cl₂·22H₂O (3) were synthesized and characterized by X-ray single crystal analysis, IR spectroscopy, ESI-MS, and by solid-state stripping voltammetry. The encapsulation of trans-[Co(tn)₂Cl₂]⁺ within the cavity of CB[8] stabilizes the complex toward ligand substitution reactions in aqueous solution. The electrochemical study demonstrates that CB[8] prefers the oxidized species in trans-[Co(tn)₂Cl₂]⁺/trans-[Co(tn)₂Cl₂]⁰ and trans-[Co(tmO)(tmOH)₂]²⁺/trans-[Co(tmO)(tmOH)₂]⁺ redox couples, but stabilizes the reduced form trans-[Ni(tmOH)₂]²⁺ against the oxidized species. The reversibility of voltammogram shapes evidence that for the inclusion compounds 1−3 electron transfer reactions proceed within the cavity of the host.