Abstract
A dynamic combinatorial library (DCL) was formed by mixing the triamine 1 and the diamine 3 with the pyridine‐2,6‐dicarbaldehyde 2 (R = OMe). In the absence of any template ion, the bimacrocyclic cage 4 (R = OMe) derived from the triamine 1 formed nicely whereas the monomacrocycle 5 (R = OMe) originating from the diamine 3 was only formed in small amounts (product ratio, after reduction: [6]/[7] = 4.3:1). Addition of calcium ions reversed the product ratio ([6]/[7] = 1:17).

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