Issue 24, 2024

Linker installation transformations in a 2-D rare earth MOF: increase of the dimensionality and turn on of the temperature sensing capability

Abstract

A new family of 2-D 8-connected rare earth (RE) MOFs based on a hexanuclear (RE3+)6 secondary building unit (SBU), the increase of the dimensionality through single-crystal-to-single-crystal (SCSC) linker installation reactions and the turn-on of the temperature sensing capability upon these reactions are reported. The reaction of RE(NO3)3 with 4,4′-(hydroxymethylene)dibenzoic acid (H2BCPM) in the presence of 2-fluorobenzoic acid (HFBA) in DMF/H2O at 115 °C afforded compounds [RE63-OH/F)8(BCPM)4(NO3)2(H2O)4]n (UCY-17(RE); RE: Y, Gd, Tb, Dy, Ho, Er) which represent rare examples of 2D 8-c MOFs based on a hexanuclear (RE3+)6 SBU. The excellent quality of single crystals of UCY-17(Tb) and the distance between the terminal nitrate ions prompted us to investigate the SCSC exchange of NO3 anions by various dicarboxylate ligands aiming to bridge adjacent 2D nanosheets and form 3-D analogues. These SCSC linker installation reactions afforded a series of 3-D, 10-connected mixed linker MOFs with the general formulae [RE63-OH/F)8(BCPM)4(L)(H2O)4]n (UCY-17(Tb)/L; H2L = H2BDC (1,4-benzenedicarboxylic acid), H2ABDC (2-aminobenzene-1,4-dicarboxylic acid), H2FBDC (2-fluorobenzene-1,4-dicarboxylic acid), and H2NDC (1,4-naphthalenedicarboxylic acid)). The exchanged analogues of UCY-17(Gd) and UCY-17(Eu0.05Tb0.95) were synthesized and the thermometric properties of the latter were investigated. These studies revealed that there is no thermal evolution of the emission properties for the pristine MOF UCY-17(Eu0.05Tb0.95) whereas the exchanged analogues exhibit significant thermometric properties at higher temperatures (>270 K). The maximum thermal sensitivity of most exchanged derivatives appears at physiological temperatures and ranges between 300 and 355 K. Overall, this work proposes a promising strategy for increasing the dimensionality of 2-D MOFs and controlling the thermometric performances of mixed Eu0.05Tb0.95 MOFs.

Graphical abstract: Linker installation transformations in a 2-D rare earth MOF: increase of the dimensionality and turn on of the temperature sensing capability

Supplementary files

Article information

Article type
Paper
Submitted
12 Mar 2024
Accepted
26 Apr 2024
First published
26 Apr 2024
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. C, 2024,12, 8684-8696

Linker installation transformations in a 2-D rare earth MOF: increase of the dimensionality and turn on of the temperature sensing capability

L. K. Komodiki, N. Panagiotou, H. Serier-Brault and A. J. Tasiopoulos, J. Mater. Chem. C, 2024, 12, 8684 DOI: 10.1039/D4TC00992D

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