14-, 30-, and 56-Membered Azamacrocyclic Mannich Bases Built on Bispyrrolylphenylene Platforms: Isolation and Initial Anion Binding

A hitherto unknown class of 14 (3)-, 30 (5)-, and 56-membered (4) azamacrocycles containing bispyrrolylphenylene moieties was synthesized via Mannich reactions and characterized by spectroscopic and crystallographic techniques. Among the observed [1 + 1 + 2], [2 + 2 + 4], [3 + 3 + 6], and [4 + 4 + 8] combinations of incorporated reactants in the crude product(s), three were isolated in pure forms. Acetate ions constrained in close proximity within the compartments of the di ([5H₂]²⁺)- and tetraprotonated ([4H₄]⁴⁺) macrocycles and one such complex existed in a dynamic equilibrium in solution.