Transmetalation and Demetallization for Open-Oyster-like Non-Ionic Cd(II) Macrocycles

• Published in: Inorganic chemistry Vol. 59; no. 11; pp. 7504 - 7511
• Main Authors: Zhao, Pei-Chen, Chang, Fei-Fan, Feng, Fan-Da, Huang, Wei
• Format: Journal Article
• Language: English
• Published: United States 01.06.2020
• ISSN: 0020-1669; 1520-510X; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c00304

This work designed a nonionic extended dialdehyde 6,6'-(phenylazanediyl)dipicolinaldehyde ( ) for constructing Schiff-base macrocyclic complexes with weaker metal-ligand interactions, so as to solve the long-standing challenges of transmetalation and demetallization in macrocyclic complexes. An enantiomeric pair of open-oyster-like 26-membered [2 + 2] Schiff-base macrocyclic dinuclear Cd(II) complexes ( , - , , - ) could be obtained, having , / , -1,2-diaminocyclohexane ( , / , - ) precursors, while Cu(II) ion template only resulted in a mononuclear Schiff-base Cu(II) acyclic complex ( , - ) accompanied by the half-oxidation of instead of expected [2 + 2] Cu(II) macrocyclic complexes. It is suggested that the weak oxidization capability of Cu(II) ion is responsible for the formation of , - because X-ray photoelectron spectroscopy (XPS) for the solid powder of reaction mixture of direct Cu(II) ion template synthesis implies that both Cu(I) and Cu(II) species are present. In fact, corresponding [2 + 2] dinuclear Cu(II) macrocycles and even metal-free macrocycles unsuitable for direct synthesis can be obtained via Cd(II) → Cu(II) transmetalation and Na S demetalation verified by ESI-MS and UV-vis spectra. In addition, control experiments indicate that the synthesis of metal-free macrocycles via the direct nontemplate method merely results in the mixture of multiple components of [1 + 1], [2 + 2], and [3 + 3] Schiff-base macrocycles, and they are difficult to isolate.