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

Abstract

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) 2Cl 2]@CB[8]}Cl.14H 2O ( 1), { trans-[Co(tmOH)(tmO)]@CB[8]}Cl 2.22H 2O ( 2), and { trans-[Ni(tmOH) 2]@CB[8]}Cl 2.22H 2O ( 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) 2Cl 2] (+) 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) 2Cl 2] (+)/ trans-[Co(tn) 2Cl 2] (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.