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

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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
Issue number4
Publication statusPublished - Feb 16 2015


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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