Solvent effects in thermodynamically controlled multicomponent nanocage syntheses

Abstract

The solvent effects on the condensation reaction between tetraformylcavitand 2 and ethylene-1,2-diamine 3 are reported. Earlier, it was found that the trifluoroacetic acid-catalyzed condensation of 2 and 2 equiv of 3 in CHCl(3) provides in 82% yield an octahedral nanocage 1 composed of 6 cavitands that are linked together by 12 -CH=N-CH(2)CH(2)-N=CH- linker groups (Liu, X.; Liu, Y.; Li, G.; Warmuth, R. Angew. Chem., Int. Ed. 2006, 45, 901). In tetrahydrofuran, the same reactants yield a tetrameric nanocage 4 (35% yield), which resembles a distorted tetrahedron built up from four cavitands that occupy the apexes. Each cavitand is doubly linked to one other cavitand and singly linked to the other two cavitands via -CH=N-CH(2)CH(2)N=CH- connectors. In CH(2)Cl(2), the reaction between 8 2 and 16 3 yields a square antiprismatic nanocage 5 (65% yield), in which each cavitand occupies one of the eight corners and is connected to four neighboring cavitands via -CH=N-CH(2)CH(2)-N=CH- linkers. Nanocage 5 is also the main product in CH(2)ClCH(2)Cl (26% yield) and CHCl(2)CHCl(2) (33% yield). Reduction of all imine bonds in 4 and 5 yields polyaminonanocontainers 7 and 8, respectively, which were isolated as trifluoroacetate salts. Contrary to the formation of larger capsules composed of four, six, or eight cavitands in the reaction between 2 and 3, the acid-catalyzed reaction of 2 with 2 equiv of H(2)N-X-NH(2) (X = (CH(2))(n)(=3,4,5), 1,3-C(6)H(4), 1,4-(CH(2))(2)C(6)H(4), or 1,3-(CH(2))(2)C(6)H(4)) quantitatively yields octaiminohemicarcerands 9-14, in which two cavitands are connected with four -CH=N-X-N=CH- linkers. The outcomes of these condensation reactions are rationalized with the different diamine structures and the relative orientation of cavitands in 1, 4, 5, and 9-14.