Exceptional thermal stability of lanthanide-phosphonate frameworks

resumo

A single-crystal-to-single-crystal transformation (SC-SC) of [Ln(H5btp)]2H2O [where Ln3+ = Gd3+ (1Gd), Tb3+ (1Tb), Dy3+ (1Dy), Ho3+ (1Ho), Er3+ (1Er), and Tm3+ (1Tm)] led to the formation of [Ln(L)(HL)] (where L = [-(PO3)(C6H3)(PO2)] and HL = [-(PO2H)(C6H3)(PO2)]n) based on a polymeric phosphonate-based organic linker (i.e., a polyMOF). The resulting material has high thermal stability maintaining its crystallinity and structural features up to ca. 800 degrees C, thus being to date the most thermally-robust and stable MOF. This remarkable feature is attributed to the close compact 3D network maintained by the strong pyrophosphonate bridges formed by the dehydration of the material at high temperatures. A remarkable thermally-robust and stable metal-organic framework with lanthanide cations is obtained by the in situ formation of a polymeric phosphonate-based organic ligand.

palavras-chave

METAL-ORGANIC FRAMEWORKS; POLYMOFS

categoria

Materials Science; Physics

autores

Firmino, ADG; Mendes, RF; Figueira, F; Tomé, JPC; Paz, FAA

nossos autores

agradecimentos

This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, (Refs. UIDB/50011/2020, DOI 10.54499/UIDB/50011/2020; UIDP/50011/2020, DOI 10.54499/UIDP/50011/2020; LA/P/0006/2020, DOI 10.54499/LA/P/0006/2020), financed by national funds through the FCT/MCTES (PIDDAC), CQE (UIDB/00100/2020 and UIDP/00100/2020) and IMS (LA/P/0056/2020). FCT is gratefully acknowledged for the PhD grant No. SFRH/BD/84495/2012 (to D. F.) and for the Junior Research Position (https://doi.org/10.54499/CEECIND/00553/2017/CP1459/CT0034) (to R. F. M.). The research contract of F. F. (REF-168-89-ARH/2018) is funded by national funds (OE), through FCT, in the scope of the framework contract foreseen in No. 4, 5 and 6 of article 23 of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19.

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