Hybrid Organosilicon Polymers Integrating Latent Si–Si Chromophores and Orthogonal Si–O–C Reactivity
Year: 2026
Type: preprint
Abstract: A dioxasilepanyl masking strategy enables the direct incorporation of Si-Si bonds into polymer backbones via mild, atom-efficient thiol-ene polyaddition.A malic acid-derived dioxasilepane (Si(pan)) monomer stabilizes an otherwise fragile disilane motif while preserving latent chemical reactivity and embedding the Si-Si unit within a chemically addressable Si-O-C-rich organosilicon scaffold.Thermal AIBN-initiated polymerizations with aliphatic dithiols afford well-defined poly(thioether)s that retain the characteristic Si-Si absorption and remain thermally robust (T d,5% up to 290 °C).The resulting materials exhibit blue photoluminescence (λ em about 447 nm) consistent with clustering-triggered σ-σ* emission and supported by a matched smallmolecule model.The hybrid backbone further exhibits chemically differentiated responses to acidic and oxidative conditions: acidic hydrolysis cleaves Si-O-C linkages to generate alcohol-functional fragments, whereas oxidation modifies the thioether and disilane environments and produces siloxane-type species, providing preliminary pathways toward chemically programmed deconstruction.These results translate Si(pan) stabilization from molecular silylation to polymeric materials and establish a hybrid Si-Si and Si-O-C platform for luminescent and trigger-responsive organosilicon polymers. Dioxasilepane (Si(pan)), Si-Si bonds, Cluster-triggered emission, Poly(thioether)s, Trigger-responsive transformation
Source: ChemRxiv
Institutions: Helmholtz Institute Jena, Centre National de la Recherche Scientifique, Université de Haute-Alsace, Institut de Sciences des Matériaux de Mulhouse, Kyoto University, Helmholtz-Zentrum Berlin für Materialien und Energie, Leibniz-Institut für Verbundwerkstoffe GmbH, Friedrich Schiller University Jena
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7220404987