Metal Ion‐Driven Constitutional Adaptation in Dynamic Covalent C=C/C=N Organo‐Metathesis

• Published in: Chemistry, an Asian journal an Asian journal, 2021-01, Vol.16 (1), p.44-48
• Main Authors: Gu, Ruirui, Lehn, Jean‐Marie
• Format: Article
• Language: English
• Subjects: Adaptation; Cations; Chemistry; constitutional adaptation; constitutional dynamic networks; Copper; Covalence; Derivatives; dynamic covalent libraries; dynamic covalent reactions; Imines; Iron; metal ion coordination; Metal ions; Metathesis; Reagents; Silver; Zinc
• ISSN: 1861-4728; 1861-471X
• DOI: 10.1002/asia.202001001

Knoevenagel barbiturate derivatives and imines are able to undergo efficient component recombination through dynamic covalent C=C/C=N organo‐metathesis in absence of a catalyst. A [2×2] dynamic covalent library (DCL) containing two Knoevenagel derivatives Kn1 and Kn2 and two imines A1 and A2 has been established and its adaptive features in response to the addition of metal cations have been investigated. Addition of Cu(I) triflate as an effector, induces fast and remarkable constitutional selection of the DCL towards amplification of the Cu(I)‐A2 complex and its agonist Kn1. This adaptation process could be reversed by addition of neocuproine as a competitive Cu(I) ligand. Furthermore, separate addition of five other metal cations as input agents, i. e. Ag(I), Fe(II), Zn(II), Cu(II) and Li(I), led to the generation of cation‐specific distribution patterns as outputs, showing the ability of the present DCL to recognize different effectors. A specially designed four‐member dynamic covalent library (DCL) based on C=C/C=N organo‐metathesis responds to the addition of Cu(I) triflate by constitutional selection, which could be reversed by addition of neocuproine. Furthermore, cation‐specific dynamic constitutional distribution patterns of the DCL were generated on addition of different metal salts.