Endohedrally Functionalized Metal-Organic Cage-Cross-Linked Polymer Gels as Modular Heterogeneous Catalysts

Christopher M. Brown, David J. Lundberg, Jessica R. Lamb, Ilia Kevlishvili, Denise Kleinschmidt, Yasmeen S. Alfaraj, Heather J. Kulik, Maria Francesca Ottaviani, Nathan J. Oldenhuis, Jeremiah A. Johnson

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

The immobilization of homogeneous catalysts onto supports to improve recyclability while maintaining catalytic efficiency is often a trial-and-error process limited by poor control of the local catalyst environment and few strategies to append catalysts to support materials. Here, we introduce a modular heterogenous catalysis platform that addresses these challenges. Our approach leverages the well-defined interiors of self-assembled Pd12L24 metal-organic cages/polyhedra (MOCs): simple mixing of a catalyst-ligand of choice with a polymeric ligand, spacer ligands, and a Pd salt induces self-assembly of Pd12L24-cross-linked polymer gels featuring endohedrally catalyst-functionalized junctions. Semi-empirical calculations show that catalyst incorporation into the MOC junctions of these materials has minimal affect on the MOC geometry, giving rise to well-defined nanoconfined catalyst domains as confirmed experimentally using several techniques. Given the unique network topology of these freestanding gels, they are mechanically robust regardless of their endohedral catalyst composition, allowing them to be physically manipulated and transferred from one reaction to another to achieve multiple rounds of catalysis. Moreover, by decoupling the catalyst environment (interior of MOC junctions) from the physical properties of the support (the polymer matrix), this strategy enables catalysis in environments where homogeneous catalyst analogues are not viable, as demonstrated for the Au(I)-catalyzed cyclization of 4-pentynoic acid in aqueous media.

Original languageEnglish (US)
Pages (from-to)13276-13284
Number of pages9
JournalJournal of the American Chemical Society
Volume144
Issue number29
DOIs
StatePublished - Jul 27 2022

Bibliographical note

Funding Information:
C.M.B. acknowledges the Natural Sciences and Engineering Research of Canada (NSERC) for a Postdoctoral Fellowship. D.J.L. acknowledges the National Science Foundation Graduate Research Fellowship grant no. 1745302 for funding, J.R.L. acknowledges grant 1F32GM126913 for funding and N.J.O. acknowledges grant 1F32GM123710 for funding. This work was supported by the NSF Center for the Chemistry of Molecularly Optimized Networks (MONET), CHE-2116298.

Publisher Copyright:
© 2022 American Chemical Society.

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

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