Mechanochemical Synthesis of Metallophenylsiloxanes Based on Polyphenylsiloxane and Acetylacetonates of Rare Earth Metals

Abstract

The present study pioneers the investigation of mechanochemical synthesis based on polyphenylsilsesquioxane and β-diketonate complexes of scandium, yttrium, and lanthanum. It has been demonstrated that the degree of metal incorporation into the polymer chain increases with the growth of the ionic radius and with the decrease in the stability of the initial acetylacetonate complex. The resulting polymers exhibit high thermal stability, comparable to that of the parent organosilicon polymer. Moreover, owing to their developed surface area and light-transforming properties, the synthesized compounds hold promise for applications in catalysis, production of electronic materials, and fabrication of nanoelectronic components.

Keywords

Mechanochemistry / Siloxane / Rare-earth elements / Metal-containing polymers / Polyphenylsiloxane / β-diketonates

Acknowledgments

The authors express their deep gratitude to the Molecular Analysis Laboratory at the Institute of High-Tech Technologies and Advanced Materials (Far Eastern Federal University), as well as to Natalya Valeryevna Maslova, Engineer at the Department of Chemistry and Materials, for conducting several chemical analysis methods.

Author Contributions

Conceptualization, V.L. and A.K.; Methodology, V.L., I.K. and V.T.; Software, V.L.; Validation, V.L., A.K., I.K. and V.T.; Formal Analysis, V.L., I.K. and V.T.; Investigation, V.L., A.K., I.K. and V.T.; Resources, V.L. and A.K.; Data Curation, V.L. and A.K.; Writing—Original Draft Preparation, V.L.; Writing—Review & Editing, V.L. and A.K.; Supervision, V.L. and A.K.

Ethics Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

All data supporting the results of this study are contained in the supplementary materials to the article, available at: www.sciepublish.com/xxx/s1. Additional data, including raw files obtained during the study using instrument-specific software, as well as author-related information, may be accessed upon request to the corresponding author. Requests will be reviewed on a case-by-case basis, subject to applicable restrictions.

Funding

This research received no external funding.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References

[1] Raygorodsky I, Kopylov V, Kovyazin A . Membrane Materials for Gas and Vapor Separation; Wiley: Hoboken, NJ, USA, 2017; pp. 17-51.

[2] Pielichowski K, Njuguna J, Janowski B, Pielichowski J . Supramolecular Polymers Polymeric Betains Oligomers. Advances in Polymer Science; Springer: Berlin/Heidelberg, Germany, 2006; Volume 201, pp. 225-296. DOI: 10.1007/12_077

[3] Khoroshavina JV, Frantsuzova JV, Nikolaev GA . The properties of vulcanisates based on a polyphenylsilsesquioxane—polydimethylsiloxane block copolymer. Int. Polym. Sci. Technol. 2015, 42, 13-16. DOI: 10.1177/0307174x1504200903

[4] O’Lenick AJ . Silicone Polymers: New Possibilities in Nanotechnology. ACS Symp. Ser. 2007, 961, 165-175. DOI: 10.1021/bk—2007—0961.ch009

[5] Anisimov AA, Minyaylo EO, Shakirova AR, Shchegolikhina OI . Evolution of Organometallasiloxanes. Polym. Sci. 2023, 65, 230-258. DOI: 10.1134/S181123822370042X

[6] Lindner E, Schreiber R, Schneller T, Wegner P, Mayer HA, Göpel W, et al. Synthesis of Polysiloxane—Bound (Ether—phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases. Inorg. Chem. 1996, 35, 514-525. DOI: 10.1021/ic950412m

[7] Lu Z, Lindner E, Mayer HA . Applications of sol—gel—processed interphase catalysts. Chem. Rev. 2002, 102, 3543-3578. DOI: 10.1021/cr010358t

[8] Racles C, Silion M, Iacob M . Lanthanum complex of a multifunctional water—soluble siloxane compound—Synthesis, surface activity and applications for nanoparticles stabilization. Colloids Surf. A Physicochem. Eng. Asp. 2014, 462, 9-17. DOI: 10.1016/j.colsurfa.2014.08.016

[9] Feng J, Zhang H . Hybrid materials based on lanthanide organic complexes: A review. Chem. Soc. Rev. 2013, 42, 387-410. DOI: 10.1039/c2cs35069f

[10] Kim EE, Kononevich YN, Dyuzhikova YS, Ionov DS, Khanin DA, Nikiforova GG, et al. Cross—Linked Luminescent Polymers Based on β—Diketone—Modified Polysiloxanes and Organoeuropiumsiloxanes. Polymers 2022, 14, 2554. DOI: 10.3390/polym14132554

[11] Kim EE, Ershova TO, Belova AS, Khanin DA, Bashkova EV, Nikiforova GG, et al. Luminescent Composite Films Based on Mechanically Strong Ladder—like Polyphenylsilsesquioxane and Oligophenyleuropiumsiloxane. Chin. J. Polym. Sci. 2024, 42, 1793-1801. DOI: 10.1007/s10118—024—3190—9

[12] Hasegawa Y, Kawai H, Nakamura K, Yasuda N, Wada Y, Yanagida S . Molecular design of luminescent Eu(III) complexes as lanthanide lasing material and their optical properties. J. Alloys Compd. 2006, 408—412, 669-674. DOI: 10.1016/j.jallcom.2004.12.145

[13] Manseki K, Hasegawa Y, Wada Y, Yanagida S . Photophysical properties of tetranuclear Eu(III) complexes in polyphenylsilsesqioxane (PPSQ). J. Alloys Compd. 2006, 408—412, 805-808. DOI: 10.1016/j.jallcom.2005.01.071

[14] Andropova US, Aysin RR, Serenko OA, Ershova TO, Anisimov AA, Chernik VN . Ladder Polyphenylsilsesquioxanes and Their Niobium—Siloxane Composite as Coating Materials: Spectroscopy and Atomic Oxygen Resistance Study. Polymers 2023, 15, 3299. DOI: 10.3390/polym15153299

[15] Howard JL, Cao Q, Browne DL . Mechanochemistry as an emerging tool for molecular synthesis: What can it offer? Chem. Sci. 2018, 9, 3080-3094. DOI: 10.1039/c7sc05371a

[16] Friscic T, Mottillo C, Titi HM . Mechanochemistry for Synthesis. Angew. Chem. Int. Ed. 2020, 59, 1018-1029. DOI: 10.1002/anie.201906755

[17] Hu L, Xu S, Zhao Z, Yang Y, Peng Z, Yang M, et al. Ynamides as Racemization—Free Coupling Reagents for Amide and Peptide Synthesis. J. Am. Chem. Soc. 2016, 138, 13135-13138. DOI: 10.1021/jacs.6b07230

[18] Atapalkar RS, Kulkarni AA . Batch and continuous flow mechanochemical synthesis of organic compounds including APIs. React. Chem. Eng. 2024, 9, 10-25. DOI: 10.1039/D2RE00521B

[19] Arkhipov IA, Dushkin AV, Khalikov SS, Varlamova AI, Arisov MV, Glamazdin II, et al. The effect of mechanochemical technology on the anthelmintic efficacy of solid dispersion of albendazole. Biopharm. J. 2021, 13, 36-41. Available online: https://www.researchgate.net/publication/351214810_Vlianie_mehanohimiceskoj_tehnologii_na_antigelmintnuu_effektivnost_tverdoj_dispersii_albendazola (accessed on 11 February 2026). (In Russian)

[20] Khalikov SS, Dushkin AV . Strategies for solubility enhancement of anthelmintics (Review). Pharm. Chem. J. 2020, 54, 504-508. DOI: 10.1007/s11094—020—02229—4

[21] Wei W, Evseenko VI, Khvostov MV, Borisov SA, Tolstikova TG, Polyakov NE, et al. Solubility, Permeability, Anti—Inflammatory Action and In Vivo Pharmacokinetic Properties of Several Mechanochemically Obtained Pharmaceutical Solid Dispersions of Nimesulide. Molecules 2021, 26, 1513. DOI: 10.3390/molecules26061513

[22] Harris N, Benedict J, Dickie DA, Pagola S . Mechanochemical synthesis insights and solid—state characterization of quininium aspirinate, a glass—forming drug—drug salt. Acta Crystallogr. Sect. C Struct. Chem. 2021, 77, 566-576. DOI: 10.1107/S2053229621008275

[23] Boyde NC, Rightmire NR, Bierschenk EJ, Steelman GW, Hanusa TP, Brennessel WW . Reaction environment and ligand lability in group 4 Cp₂MXY (X, Y = Cl, OtBu) complexes. Dalton Trans. 2016, 45, 18635-18642. DOI: 10.1039/c6dt03199d

[24] Wenger LE, Hanusa TP . Synthesis without solvent: Consequences for mechanochemical reactivity. Chem. Commun. 2023, 59, 14210-14222. DOI: 10.1039/D3CC04929A

[25] Leonardi M, Villacampa M, Menéndez JC . Multicomponent mechanochemical synthesis. Chem. Sci. 2018, 9, 2042-2064. DOI: 10.1039/C7SC05370C

[26] Takahashi R, Gao P, Kubota K, Ito H . Mechanochemical protocol facilitates the generation of arylmanganese nucleophiles from unactivated manganese metal. Chem. Sci. 2023, 14, 499-505. DOI: 10.1039/d2sc05468j

[27] Levitskii MM, Smirnov VV, Zavin BG, Bilyachenko AN, Rabkina AY . Metalasiloxanes: new structure formation methods and catalytic properties. Kinet. Catal. 2009, 50, 490-507. DOI: 10.1134/S0023158409040041

[28] Chen Y, Mellot G, van Luijk D, Creton C, Sijbesma RP . Mechanochemical tools for polymer materials. Chem. Soc. Rev. 2021, 50, 4100-4140. DOI: 10.1039/d0cs00940g

[29] Kapustina AA, Libanov VV, Shapkin NP, Pobozhev KV . The study of the interaction of aluminum acetylacetonate with polyphenylsilsesquioxane with the help of mechanochemical activation. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2022, 65, 59-66. DOI: 10.6060/ivkkt.20226512.6660

[30] Anderson TJ, Neuman MA, Melson GA . Coordination Chemistry of Scandium. V. Crystal and Molecular Structure of tris(Acetylacetonato)scandium(III). Inorg. Chem. 1973, 12, 927-930. DOI: 10.1021/ic50122a046

[31] Cunningham JA, Sands DE, Wagner WF . Crystal and Molecular Structure of Yttrium Acetylacetonate Trihydrate. Inorg. Chem. 1967, 6, 499-503. DOI: 10.1021/ic50049a014

[32] Gavrilenko VV, Chekulaeva LA, Savitskaya IA, Garbuzova IA . Synthesis of yttrium, lanthanum, neodymium, praseodymium, and lutetium alkoxides and acetylacetonates. Russ. Chem. Bull. 1992, 41, 1957-1959. DOI: 10.1007/BF00863354

[33] Libanov V, Kapustina A, Shapkin N, Puzyrkov Z, Dmitrinok P . Mechanochemical synthesis of Polyboronphenylsiloxanes. Polymer 2020, 194, 122367. DOI: 10.1016/j.polymer.2020.122367

[34] Kapustina AA, Shapkin NP, Libanov VV . Preparation of polyboronphenylsiloxanes by mechanochemical activation. Russ. J. Gen. Chem. 2014, 84, 1320-1324. DOI: 10.1134/S1070363214070123

[35] Libanov VV, Kapustina AA, Shapkin NP, Rumina AA . Mechanochemical interaction of boron difluoride acetylacetonate with organosilicon derivatives of different functionality. Silicon 2019, 11, 1489-1495. DOI: 10.1007/s12633—018—9969—y