Mechanochemical synthesis and structure of a nanocluster {organosilicon dendrimer - Copper dimer}

• Published in: Journal of organometallic chemistry 2021-10, Vol.950, p.121976, Article 121976
• Main Authors: Aleksandrov, Aleksey I., Shevchenko, Vitaliy G., Tarasenkov, Aleksandr N., Surin, Nikolai M., Cherkaev, Georgiy V., Metlenkova, Irina Yu, Svidchenko, Evgeniya A., Krasovsky, Vladimir G., Dubinsky, Aleksandr A., Degtyarev, Evgeniy N.
• Format: Article
• Language: English
• Subjects: Carbosilane dendrimers; Complexation; Copper (II) chloride; Mechanochemistry; Monomer; Nanocluster; Quantum chemical analysis; Sulfur-containing dendrimers
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2021.121976

•One-stage mechanochemical synthesis of a chemically stable nanocluster in dendrimer by the method of mechanoactivation.•The proposed approach greatly simplifies the process of nanostructure synthesis by the guest - host type, reducing it to one stage.•Dendrimer stabilizes the binuclear copper complex with the Dzyaloshinsky-Moriya effect. A novel nanocluster (organosilicon dendrimer - copper dimer) G1–8S-Dec•2CuCl2 was synthesized by a mechanochemical method. Optical and IR spectroscopy, NMR and ESR methods confirm that mechanochemical action on the mixture (dendrimer G1–8S-Dec + anhydrous copper (II) chloride) leads to the formation of a structure in which two copper atoms are linked by exchange interaction and are stabilized in the form of a dimer by sulfur atoms in the structure of the dendrimer G1–8S-Dec. A quantum mechanical calculation was carried out using the density differential method (DFT), which proved the possibility of the existence of two tetrahedral complexes SCuCl3 connected by a common face of chlorine atoms and having sulfur atoms at the vertices located in the branches of the dendrimer. The structure of the Cu2Cl4Si5C116H244S8 nanocluster is calculated by complete geometry optimization. It was found that the synthesized cluster implements the Dzyaloshinsky - Moriya interaction and exhibits multiferroic properties. [Display omitted]