Syntheses, structures, and electrochemical properties of inclusion compounds of cucurbit[8]uril with cobalt(III) and nickel(II) complexes

Inclusion compounds of a macrocyclic cavitand cucurbit8]uril (CB8]) with cobalt(III) and nickel(II) complexes of 1,3-diaminopropane (tn) and 1,3-diamino-2-propanol (tmOH) { trans-Co(tn) 2Cl 2]@CB8]}Cl.14H 2O ( 1), { trans-Co(tmOH)(tmO)]@CB8]}Cl 2.22H 2O ( 2), and { trans-Ni(tmOH) 2]@CB8]}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 CB8] stabilizes the complex toward ligand substitution reactions in aqueous solution. The electrochemical study demonstrates that CB8] 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.