Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs

Pravas Deria, Diego A. Gómez-Gualdrón, Idan Hod, Randall Q. Snurr, Joseph T. Hupp, Omar K. Farha

Research output: Contribution to journalArticle

74 Citations (Scopus)

Abstract

Catalytic activity for acyl transfer from N-acetylimidazole (NAI) to different pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC) is demonstrated for a set of topologically diverse, zirconium-based (porphinato)zinc metal-organic frameworks (MOFs). The MOFs studied are PCN-222, MOF-525, and NU-902, which are based on the csq, ftw, and scu topologies, respectively. The experimentally obtained reaction kinetics are discussed in light of molecular modeling results. The catalytic activity is shown to vary across the series of MOFs due to the different extent to which each topology facilitates reactant preconcentration and alignment of PC and NAI via coordination to framework porphyrin sites (orientation effects). Trends of experimental initial reaction rates with MOF topology and PC regioisomer are consistent with preconcentration effects, which depend on the number of porphyrin sites per volume of MOF, as well as with orientation effects, which depend on the number of porphyrin pairs per volume of MOF that bind PC and NAI in such a way that they are primed to form the required transition state. The present work shows how the proper alignment of catalytic linkers can enhance reaction rates in MOFs.

Original languageEnglish
Pages (from-to)14449-14457
Number of pages9
JournalJournal of the American Chemical Society
Volume138
Issue number43
DOIs
Publication statusPublished - Nov 2 2016

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Nicotinyl Alcohol
Zirconium
Zinc
Catalyst activity
Metals
Topology
Porphyrins
Reaction rates
Pregnenolone Carbonitrile
Molecular modeling
Reaction kinetics

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs. / Deria, Pravas; Gómez-Gualdrón, Diego A.; Hod, Idan; Snurr, Randall Q.; Hupp, Joseph T.; Farha, Omar K.

In: Journal of the American Chemical Society, Vol. 138, No. 43, 02.11.2016, p. 14449-14457.

Research output: Contribution to journalArticle

Deria, Pravas ; Gómez-Gualdrón, Diego A. ; Hod, Idan ; Snurr, Randall Q. ; Hupp, Joseph T. ; Farha, Omar K. / Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 43. pp. 14449-14457.
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