Ferrocene-Cored Poly(aryl ether) Dendritic Organometallic Gels: Multi-Stimuli-Responsive Properties and Efficient Heavy Metal Ion Adsorption

doi:10.6023/A26070257

Abstract

Developing supramolecular gels that effectively integrate multi-stimuli responsiveness with high-performance heavy metal adsorption remains a significant challenge, primarily due to the limited functionality and weak synergistic effects of conventional gelators. To address this issue, we have designed and synthesized two novel ferrocene-cored poly(aryl ether) dendritic organometallic gelators, designated as FC-D1 and FC-D2, which are functionalized with amide and acylhydrazide linkages. The chemical structures of both gelators were thoroughly characterized using standard spectroscopic techniques. Our experimental results demonstrate that both FC-D1 and FC-D2 exhibit outstanding gelation ability across a broad spectrum of pure organic solvents and binary solvent mixtures, forming highly stable organogels at remarkably low critical gelation concentrations (CGC). Mechanistic investigations employing Fourier-transform infrared (FT-IR) spectroscopy and variable-concentration proton nuclear magnetic resonance (¹H NMR) spectroscopy reveal that the self-assembly process is synergistically driven by two key non-covalent interactions: intermolecular hydrogen bonding originating from the acylhydrazone and amide moieties, and π-π stacking interactions among the aromatic rings of the dendritic branches. This cooperative assembly leads to the formation of robust three-dimensional network structures. The resulting metallogels exhibit excellent and reversible multi-stimuli-responsive properties, enabling reliable gel-to-sol transitions upon exposure to various external stimuli, including temperature changes, redox reactions (using ceric ammonium nitrate (CAN) and glutathione (GSH) as an oxidizing/reducing pair), chemical triggers (specifically fluoride ions), and mechanical thixotropic stimuli. Beyond their stimuli-responsive behavior, we also evaluated the potential of the FC-D1 dendron as an effective and recyclable adsorbent for the removal of toxic heavy metal ions from aqueous environments. The results show that FC-D1 achieves impressive removal efficiencies of 72%, 51%, and 73% for Hg²⁺, Pb²⁺, and Cd²⁺, respectively. Furthermore, the gel system maintains stable adsorption performance over four consecutive adsorption-desorption cycles, demonstrating good reusability. Overall, this work not only provides a new and effective molecular design strategy for constructing multifunctional dendritic organometallic gels but also significantly expands their potential applications in the fields of intelligent sensing and heavy metal wastewater remediation.

Key words: Organometallic gel, Multi-stimuli-responsive, Dendrimer, self-assembly, Heavy metal adsorption

Cite this article

Hongkui Zhang, Bo Jiang, Hua Zhang, Rui Li, Yu Feng. Ferrocene-Cored Poly(aryl ether) Dendritic Organometallic Gels: Multi-Stimuli-Responsive Properties and Efficient Heavy Metal Ion Adsorption[J]. Acta Chimica Sinica, doi: 10.6023/A26070257.

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