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PreprintCC BYChemRxiv

Hybrid Organosilicon Polymers Integrating Latent Si–Si Chromophores and Orthogonal Si–O–C Reactivity

  • Bercis Pektas1,2
  • Cuong Minh Quoc Le1
  • Kenshiro Hitoshio3
  • Hideki Yorimitsu3
  • Jun Shimokawa3
  • Hatice Mutlu1,2,4,5,6
6 affiliations
  1. 1Institut de Science des Matériaux de Mulhouse (IS2M), UMR 7361 CNRS/Université de Haute Alsace (UHA), 15 rue Jean Starcky, Mulhouse, France, 68057
  2. 2Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena), Lessingstr. 12-14, Jena, Thuringen, Germany, 07743
  3. 3Department of Chemistry Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto, Japan, 606-8502
  4. 4Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, Jena, Thuringen, Germany, 07743
  5. 5Helmholtz-Zentrum Berlin for Materials and Energy GmbH, Hahn-Meitner-Platz 1, Berlin, Berlin, Germany, 14109
  6. 6Leibniz-Institut für Verbundwerkstoffe (IVW) GmbH , Erwin-Schrödinger-Straße 58, Gebäude 58, Kaiserslautern, Rheinland Pfalz, Germany, 67663
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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

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Cite

BibTeXRIS
BibTeX
@misc{pektas2026hybrid,
  title = {{Hybrid Organosilicon Polymers Integrating Latent Si–Si Chromophores and Orthogonal Si–O–C Reactivity}},
  author = {Bercis Pektas and Cuong Minh Quoc Le and Kenshiro Hitoshio and Hideki Yorimitsu and Jun Shimokawa and Hatice Mutlu},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15009875/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009875/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Hybrid Organosilicon Polymers Integrating Latent Si–Si Chromophores and Orthogonal Si–O–C Reactivity
AU  - Bercis Pektas
AU  - Cuong Minh Quoc Le
AU  - Kenshiro Hitoshio
AU  - Hideki Yorimitsu
AU  - Jun Shimokawa
AU  - Hatice Mutlu
PY  - 2026
DA  - 2026/10/05
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009875/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009875/v1
AB  - 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
ER  -