Pseudo-octahedral M(II) 6 L4 capsules result from the subcomponent self-assembly of 2-formylphenanthroline, threefold-symmetric triamines, and octahedral metal ions. Whereas neutral tetrahedral guests and most of the anions investigated were observed to bind within the central cavity, tetraphenylborate anions bound on the outside, with one phenyl ring pointing into the cavity. This binding configuration is promoted by the complementary arrangement of the phenyl rings of the intercalated guest between the phenanthroline units of the host. The peripherally bound, rapidly exchanging tetraphenylborate anions were found to template an otherwise inaccessible capsular structure in a manner usually associated with slow-exchanging, centrally bound agents. Once formed, this cage was able to bind guests in its central cavity.