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

• Published in: Polymer journal 2022-08, Vol.54 (8), p.985-993
• Main Authors: Sato, Yohei, Hayami, Ryohei, Yamamoto, Kazuki, Gunji, Takahiro
• Format: Article
• Language: English
• Subjects: 639/638/263/406; 639/638/455/955; Aluminum; Biomaterials; Bioorganic Chemistry; Chemical synthesis; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Coordination polymers; Copper; Morphology; Original Article; Polyhedral oligomeric silsesquioxane; Polymer Sciences; Polymers; Scanning electron microscopy; Spectrum analysis; Surfaces and Interfaces; Thin Films; Titanium
• ISSN: 0032-3896; 1349-0540
• DOI: 10.1038/s41428-022-00651-x

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(OCOCH 3 ) 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 [Ti 2 O 2 ] 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. In this work, POSS with an acetylacetonato group (POSS-acac) and metal–coordination polymers comprising POSS-acac (CP(Metal)s) were synthesized. The possible structure of CP(Metal)s was estimated from the UV–Vis spectrum and the residual mass after burning off and the surface morphologies of the CP(Metal)s were observed using scanning electron microscopy.