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Syntheses and properties of Cu(II), Al(III), and Ti(IV) coordination polymers using an acetylacetonato-terminated polyhedral oligomeric silsesquioxane

Abstract

Synthesis of coordination polymers based on polyhedral oligomeric silsesquioxane (POSS) has attracted attention as an important research direction because POSS-based polymers can be used for element blocks. In this work, a POSS with an acetylacetonato group (POSS-acac) and metal–coordination polymers comprising POSS-acac (CP(Metal)s) were synthesized. POSS-acac was synthesized by the thiol–ene reaction of mercaptopropyl-terminated POSS with 3-allylacetylacetone. CP(Metal)s were synthesized by mixing POSS-acac and metal sources such as Cu(OCOCH3)2, Ti(OiPr)4, and Al(OiPr)3. CP(Metal)s were composed of a POSS core structure and the enolate of an acetylacetonato moiety, as determined by infrared spectroscopy. The likely structure of CP(Metal)s was estimated from the UV–Vis spectrum, and the residue left after burning contained [POSS-acac][Cu]2.3, [POSS-acac][Ti(OiPr)2]2.5[Ti2O2]0.5, and [POSS-acac][Al]2.3. The surface morphologies of the CP(Metal)s were observed using scanning electron microscopy. CP(Ti) and CP(Al) exhibited a three-dimensional network; in contrast, CP(Cu) showed a flattened surface morphology. These morphologies were induced by the polymer structure.

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Funding

This work was supported by JSPS KAKENHI Grant Numbers JP18K14287 and JP19K05636.

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YS: Investigation, conceptualization, visualization, methodology, writing–original draft. RH: Conceptualization, writing–review and editing. KY: Funding acquisition and supervision. TG: Writing–review and editing, funding acquisition, and supervision.

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Correspondence to Yohei Sato or Takahiro Gunji.

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Sato, Y., Hayami, R., Yamamoto, K. et al. Syntheses and properties of Cu(II), Al(III), and Ti(IV) coordination polymers using an acetylacetonato-terminated polyhedral oligomeric silsesquioxane. Polym J 54, 985–993 (2022). https://doi.org/10.1038/s41428-022-00651-x

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