Search

The copolymerization of two or more monomers produces polymeric materials with unique properties that cannot be achieved with homopolymers. However, precise control over the polymer sequence remains challenging because the sequence is determined by the inherent reactivity of comonomers. Therefore, only limited methods using modified monomers or supramolecular interactions are reported. In this study, the sequence control of acrylate‐styrene copolymerization using multinuclear zinc complexes is reported. The copolymerization of the zinc acrylate complex with a polymeric sheet‐like structure and styrene in benzene affords a copolymer with a higher content of acrylate triad than calculated for the statistical random model, whereas tetranuclear zinc acrylate (TZA) affords a copolymer with fewer adjacent acrylate sequences. The copolymer with a higher content of acrylate triad exhibits a lower glass transition temperature because of the higher mobility of the longer polystyrene segments. These results highlight the promise of multinuclear zinc acrylate complexes as monomers for sequence‐controlled copolymerization. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis of different shapes of complexes using zinc (meth)acrylate. The recrystallization of zinc methacrylate resulted in a macrocyclic dodecanuclear complex, while zinc acrylate formed a sheet-like pentanuclear core. Treating zinc (meth)acrylate with ZnO produced a tetranuclear complex. The article provides more detailed information on these findings. [Extracted from the article]

Zinc carboxylate complexes are widely utilized as artificial models of metalloenzymes and as secondary building units of PCPs/MOFs. However, the relationship between the structure of the monodentate carboxylato ligand and the molecular arrangement of multinuclear zinc carboxylate complexes is not fully understood because of the coordination flexibility of the Zn ion and carboxylato ligands. Herein, we report the structural analysis of a series of complexes derived from zinc (meth)acrylate which has a linear infinite chain structure. The molecular structure of μ 4 -oxido-bridged tetranuclear complexes [Zn 4 (μ 4 -O)(OCOR) 6 ] revealed a distorted Zn 4 O core. Crystallization of zinc acrylate under aqueous conditions afforded a μ 3 -hydroxido-containing pentanuclear complex [Zn 5 (μ 3 -OH) 2 (OCOR) 8 ] as the repeating unit of an infinite sheet-like structure in the solid state. It was also obtained by the hydrolysis of the μ 4 -oxido-bridged tetranuclear complex. In sharp contrast, the methacrylate analog retained the methacrylato ligands under aqueous crystallization conditions to form a macrocyclic dodecanuclear complex with methacrylato as the sole ligand., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)