Two Types of Anion-Induced Reconstruction of Schiff-Base Macrocyclic Zinc Complexes: Ring-Contraction and Self-Assembly of a Molecular Box

Two 46-membered [2 + 2] Schiff-base macrocyclic dinuclear Zn­(II) complexes (<b>1a</b> and <b>1b</b>) were investigated deeply by the postmodification strategy, and two types of supramolecular processes (ring-contraction and self-assembly) have been achieved after the addition of specific anions as stimulus for the equilibrium of Schiff-base macrocyclic complexes. Namely, in the presence of linear three-atom SCN^–, <b>1a</b> was degraded into two 23-membered [1 + 1] Schiff-base macrocyclic complexes simultaneously (mononuclear Zn­(II) complex <b>2</b> and dinuclear Zn­(II) complex <b>3</b>). In contrast, <b>1b</b> was only transformed into the macrocyclic mononuclear complex <b>5</b>. More interestingly, in the case of pseudolinear five-atom N­(CN)₂^–, supramolecular self-assembly took place instead of the above-mentioned ring-contraction. Finally, <b>1a</b> was assembled into a unique molecular box <b>4</b> with two 46-membered [2 + 2] Schiff-base macrocyclic heteronuclear Zn₄Na₄ substrates and double μ₂-N­(CN)₂^– bridges, while no similar assembly process was observed for <b>1b</b>. The geometry of anions and pH values slightly adjusted by the pendant arms on the macrocyclic skeletons are believed to be the critical factors for the different supramolecular processes originating from the dynamic covalent chemistry of Schiff-base imine bonds