The formation of carceplexes and hemicarceplexes involves an assembly
process whereby a molecular template is entrapped between two bowl-sha
ped molecules. The process can be highly selective such that a million
-fold range in template recognition has been realized. The relative te
mplate abilities, or template ratios, for 34 molecules in forming carc
eplex a guest is described. Species with one, two, and three bridges l
inking the two ''bowls'' are reported and were used to delineate the g
uest-determining step of the reaction. The effect of base and solvent
on the reaction are also described, and a discussion of the reaction m
echanism is presented.