Bifunctional porphyrin-based nano-metal-organic frameworks: Catalytic and chemosensing studies

Carla F. Pereira, Flávio Figueira, Ricardo F. Mendes, Joaão Rocha, Joseph T. Hupp, Omar K. Farha, Mário M.Q. Simoães*, Joaão P.C. Tomé, Filipe A.Almeida Paz

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

Abstract

The use of 5,10,15,20-tetrakis(p-phenylphosphonic acid)porphyrin (H10TPPA) as a linker in the preparation of porphyrin-based metal-organic frameworks (Por-MOFs) through coordination to lanthanides cations is reported. The resulting unprecedented materials, formulated as [M(H9TPPA)(H2O)x]Cl2·yH2O [x + y = 7; M3+ = La3+ (1), Yb3+ (2), and Y3+ (3)], prepared using hydrothermal synthesis, were extensively characterized in the solid-state, for both their structure and thermal robustness, using a myriad of solid-state advanced techniques. Materials were evaluated as heterogeneous catalysts in the oxidation of thioanisole by H2O2 and as chemosensors for detection of nitroaromatic compounds (NACs). Nano-Por-MOFs 1-3 proved to be effective as heterogeneous catalysts in the sulfoxidation of thioanisole, with Por-MOF 1 exhibiting the best catalytic performance with a conversion of thioanisole of 89% in the first cycle and with a high selectivity for the sulfoxide derivative (90%). The catalyst maintained its activity roughly constant in three consecutive runs. Por-MOFs 1-3 can be employed as chemosensors because of a measured fluorescence quenching up to 70% for nitrobenzene, 1,4-dinitrobenzene, 4-nitrophenol, and phenol, with 2,4,6-trinitrophenol exhibiting a peculiar fluorescence profile.

Original languageEnglish (US)
Pages (from-to)3855-3864
Number of pages10
JournalInorganic chemistry
Volume57
Issue number7
DOIs
StatePublished - Apr 2 2018

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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