Synthesis and Comparative Study of Polysiloxane Networks Cross‐Linked by Di‐ and Trivalent Metal Ions

A series of metal‐containing polysiloxane networks were synthesized using dibenzoylmethane‐functionalized precursors and various divalent (Mg 2+ , Zn 2+ , Cu 2+ ) and trivalent (Fe 3+ , Mn 3+ , Eu 3+ ) metal acetates. It was found that the use of trivalent metal ions significantly enhances the mechanical integrity of the materials, driving a transition from weak, gel‐like substances (divalent systems) to self‐standing, flexible films. Notably, the Mn 3+ ‐cross‐linked polymer exhibited a remarkable elongation at break of up to 863%, suggesting a highly dynamic coordination environment. Thermal analysis (TGA/DSC) indicated that the polymers are stable up to 300°C and demonstrate a glass transition temperature near −120°C. Furthermore, the incorporation of Eu 3+ ions provided the films with characteristic red photoluminescence. These results demonstrate that metal cross‐linking is an effective strategy for developing functional, highly elastic, and thermostable siloxane‐based materials.