Porphyrin-Metalation-Mediated Tuning of Photoredox Catalytic Properties in Metal-Organic Frameworks

Jacob A. Johnson, Jian Luo, Xu Zhang, Yu Sheng Chen, Martha D. Morton, Elena Echeverría, Fernand E. Torres, Jian Zhang

Research output: Contribution to journalArticlepeer-review

209 Scopus citations


Photoredox catalytic activation of organic molecules via single-electron transfer processes has proven to be a mild and efficient synthetic methodology. However, the heavy reliance on expensive ruthenium and iridium complexes limits their applications for scale-up synthesis. To this end, photoactive metal-organic frameworks (MOFs) exhibit unique advantages as novel heterogeneous photocatalytic systems, yet their utilization toward organic transformations has been limited. Here we describe the preparation and synthetic applications of four isostructural porphyrinic MOFs, namely, UNLPF-10a, -10b, -11, and -12, which are composed of free base, InIII-, SnIVCl2-, and SnIV-porphyrin building blocks, respectively. We demonstrate that the metalation with high valent metal cations (InIII and SnIV) significantly modifies the electronic structure of porphyrin macrocycle and provides a highly oxidative photoexcited state that can undergo efficient reductive quenching processes to facilitate organic reactions. In particular, UNLPF-12 exhibits both outstanding photostability and efficient photocatalytic activities toward a range of important organic transformations including aerobic hydroxylation of arylboronic acids, amine coupling, and the Mannich reaction.

Original languageEnglish (US)
Pages (from-to)5283-5291
Number of pages9
JournalACS Catalysis
Issue number9
StatePublished - Aug 3 2015


  • metal-organic frameworks
  • metalation
  • microporous materials
  • photocatalysis
  • porphyrins

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry


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