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Updated: Mar 28, 2026

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Published on: November 21, 2017
Two Types of Anion-Induced Reconstruction of Schiff-Base Macrocyclic Zinc Complexes: Ring-Contraction and
Kun Zhang1, Lei Zhang1, Gen-Feng Feng1
1State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, P. R. China.
Abstract:
Two 46-membered [2 + 2] Schiff-base macrocyclic dinuclear Zn(II) complexes (1a and 1b) 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(-), 1a was degraded into two 23-membered [1 + 1] Schiff-base macrocyclic complexes simultaneously (mononuclear Zn(II) complex 2 and dinuclear Zn(II) complex 3). In contrast, 1b was only transformed into the macrocyclic mononuclear complex 5. 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, 1a was assembled into a unique molecular box 4 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 1b. 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.
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