Issue 44, 2020

Nuclearity control in calix[4]arene-based zinc(ii) coordination complexes

Abstract

Three zinc-based coordination complexes were selectively generated in the crystalline phase using a new flexible molecular “tweezers” calix[4]arene derivative ligand decorated with two appended carboxylic moieties and benzyl spacers (3-4H). Through the control of the metal/ligand ratio and the synthetic conditions, the coordination sphere around the zinc cations was found to be different, which influenced the nuclearity of the obtained complexes. The mononuclear complex (3-3H)2–Zn(DMF)2 was obtained, while two partially deprotonated ligands (3-3H) cap the metallic cation, leading to a nontubular “8”-shaped structure with a metal/ligand ratio equal to 1/2. The dinuclear (3-2H)2–Zn2py4 complex displays a tubular structure with a metal/ligand ratio equal to 1/1, where two zinc cations act as a linear metal linker between two (3-2H)2− species, which adopts a cone conformation. Finally, the third trinuclear coordination complex (3-2H)4-Zn3(OH2) was obtained using (3-4H) and the highly coordinating sulfonylcalix[4]arene (4-4H), exhibiting a 3/1/1 metal/3/4 ratio. Thus, it has been demonstrated that under self-assembly conditions, the nuclearity of the new complexes based on zinc cations and calix[4]arene dicarboxylate (3-4H) can be tuned using different synthetic conditions: nature of solvent, crystallization method, use of a highly coordinating ligand (4-4H).

Graphical abstract: Nuclearity control in calix[4]arene-based zinc(ii) coordination complexes

Supplementary files

Article information

Article type
Paper
Submitted
23 août 2020
Accepted
28 sept. 2020
First published
29 sept. 2020

CrystEngComm, 2020,22, 7693-7703

Nuclearity control in calix[4]arene-based zinc(II) coordination complexes

M. V. Kniazeva, A. S. Ovsyannikov, D. R. Islamov, A. I. Samigullina, A. T. Gubaidullin, P. V. Dorovatovskii, S. E. Solovieva, I. S. Antipin and S. Ferlay, CrystEngComm, 2020, 22, 7693 DOI: 10.1039/D0CE01232G

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