Exceptional thermal stability of lanthanide-phosphonate frameworks

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abstract

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.

keywords

METAL-ORGANIC FRAMEWORKS; POLYMOFS

subject category

Materials Science; Physics

authors

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

our authors

foto Ana Daniela Gonçalves Firmino

Ana Daniela Gonçalves Firmino

Researcher
foto Filipe Alexandre Almeida Paz

Filipe Alexandre Almeida Paz

Principal Researcher
foto Flávio Alberto da Silva Figueira

Flávio Alberto da Silva Figueira

Junior Researcher
foto Ricardo Faria Mendes

Ricardo Faria Mendes

Junior Researcher

Groups

G1 - Porous Materials and Nanosystems

Projects

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

acknowledgements

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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Publication Details

type
Journal Article
year
2024
journal
JOURNAL OF MATERIALS CHEMISTRY C
volume
12
publisher
ROYAL SOC CHEMISTRY
issn
2050-7526
isbn
2050-7534
issue
38
digital object identifier
10.1039/d4tc02589j
web of science article identifier
WOS:001312779700001

Journal Metrics (JCR 2019)

Journal Impact Factor
7.059
Journal Impact Factor (5 yrs)
6.404
category normalized journal percentile
85.94

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