Functionalized defects through solvent-assisted linker exchange: Synthesis, characterization, and partial postsynthesis elaboration of a metal-organic framework containing free carboxylic acid moieties

Olga Karagiaridi, Nicolaas A. Vermeulen, Rachel C. Klet, Timothy C. Wang, Peyman Z. Moghadam, Salih S. Al-Juaid, J. Fraser Stoddart, Joseph T Hupp, Omar K. Farha

Research output: Contribution to journalArticle

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Abstract

Intentional incorporation of defect sites functionalized with free carboxylic acid groups was achieved in a paddlewheel-based metal-organic framework (MOF) of rht topology, NU-125. Solvent-assisted linker exchange (SALE) performed on a mixed-linker derivative of NU-125 containing isophthalate (IPA) linkers (NU-125-IPA) led to the selective replacement of the IPA linkers in the framework with a conjugate base of trimesic acid (H3BTC). Only two of the three carboxylic acid moieties offered by H3BTC coordinate to the Cu2 centers in the MOF, yielding a rare example of a MOF decorated with free -COOH groups. The presence of the -COOH groups was confirmed by diffuse reflectance infrared Fourier-transformed spectroscopy (DRIFTS); moreover, these groups were found to be available for postsynthesis elaboration (selective monoester formation). This work constitutes an example of the use of SALE to obtain otherwise challenging-to-synthesize MOFs. The resulting MOF, in turn, can serve as a platform for accomplishing selective organic transformations, in this case, exclusive monoesterification of trimesic acid.

Original languageEnglish
Pages (from-to)1785-1790
Number of pages6
JournalInorganic Chemistry
Volume54
Issue number4
DOIs
Publication statusPublished - Feb 16 2015

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Carboxylic Acids
carboxylic acids
Ion exchange
Metals
Defects
defects
synthesis
metals
acids
topology
platforms
Topology
Spectroscopy
Infrared radiation
Derivatives
reflectance
spectroscopy
trimesic acid
isophthalate

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Functionalized defects through solvent-assisted linker exchange : Synthesis, characterization, and partial postsynthesis elaboration of a metal-organic framework containing free carboxylic acid moieties. / Karagiaridi, Olga; Vermeulen, Nicolaas A.; Klet, Rachel C.; Wang, Timothy C.; Moghadam, Peyman Z.; Al-Juaid, Salih S.; Stoddart, J. Fraser; Hupp, Joseph T; Farha, Omar K.

In: Inorganic Chemistry, Vol. 54, No. 4, 16.02.2015, p. 1785-1790.

Research output: Contribution to journalArticle

Karagiaridi, Olga ; Vermeulen, Nicolaas A. ; Klet, Rachel C. ; Wang, Timothy C. ; Moghadam, Peyman Z. ; Al-Juaid, Salih S. ; Stoddart, J. Fraser ; Hupp, Joseph T ; Farha, Omar K. / Functionalized defects through solvent-assisted linker exchange : Synthesis, characterization, and partial postsynthesis elaboration of a metal-organic framework containing free carboxylic acid moieties. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 4. pp. 1785-1790.
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