1D–3D Coordination Polymers Based on M <sub>4</sub> Cu <sub>4</sub> -Phenylsilsesquioxane (M = K, Rb, Cs) Cages: Synthesis, Structure, and Catalytic Activity
The present study describes a convenient approach to cage-like coppersilsesquioxanes’ extended structures using large alkaline metal (K, Rb, Cs) ions as “supramolecular facilitators”. Extended family (nine examples) of Cu4-based phenylsilsesquioxane cages feature the same molecular architecture but differ principally in their supramolecular derivatives. The single-crystal X-ray diffraction analysis (SCXRD) revealed the intercage interactions due to both various alkaline metal-involved joints with solvate “linkers” (ethanol, water, acetonitrile, and acetone) and contacts between alkaline metal ions and phenyl rings of cyclic phenylsiloxanes, responsible for the generation of 1D, 2D, and 3D coordination polymers. Compound 1 was assessed as a precatalyst in the tandem oxidation of cyclohexane to ε-caprolactone. Using mCPBA as the oxidant under microwave irradiation at 80 °C for 30 min, the reaction achieved a yield of up to 31.8% of ε-caprolactone, with a high selectivity, evidencing the potential of this complex as a selective precatalyst for this one-pot process from a readily available petrochemical feedstock to a valuable industrial monomer.
Authors
- Victor N. Khrustalev (ORCID: https://orcid.org/0000-0001-8806-2975)
- Nuno Reis Conceição (ORCID: https://orcid.org/0000-0001-5102-8482)
- Maxim L. Kuznetsov (ORCID: https://orcid.org/0000-0001-5729-6189)
- Н. Н. Лобанов (ORCID: https://orcid.org/0000-0002-1954-2809)
- Fabio Marchetti (ORCID: https://orcid.org/0000-0002-3683-8708)
- Grigorii S. Astakhov (ORCID: https://orcid.org/0000-0001-6275-7832)
- Павел В. Дороватовский (ORCID: https://orcid.org/0000-0002-2978-3614)
- Elena S. Shubina (ORCID: https://orcid.org/0000-0001-8057-3703)
- Armando J. L. Pombeiro (ORCID: https://orcid.org/0000-0001-8323-888X)
- Аlexey N. Bilyachenko (ORCID: https://orcid.org/0000-0003-3136-3675)
- Ismayil M. Garazade (ORCID: https://orcid.org/0000-0002-6000-3583)
- Brij Mohan
- Alexander V. Bachinskiy
- Marco Terzaroli
Institutions
- Università di Camerino (IT)
- Peoples' Friendship University of Russia (RU)
- University of Lisbon (PT)
- Shandong University (CN)
- Baku State University (AZ)
- Kurchatov Institute (RU)
- A. N. Nesmeyanov Institute of Organoelement Compounds (RU)
- Interface (United States) (US)
- N.D. Zelinsky Institute of Organic Chemistry (RU)
- Faculty (United Kingdom) (GB)
Publication Details
- Journal
- ACS Omega
- Published
- 2026-04-27
- DOI
- https://doi.org/10.1021/acsomega.5c13068
- Primary Topic
- Silicone and Siloxane Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Russian Science Foundation
- Fundação para a Ciência e a Tecnologia