Article Postsynthetic Defect Formation in Three-Dimensional Hofmann-Type Coordination Polymers and Its Impact on Catalytic Activity

Daiki Umeyama SAMURAI ORCID (National Institute for Materials Science) ; Atsuro Takai SAMURAI ORCID (National Institute for Materials Science) ; Kazutaka Sonobe

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Daiki Umeyama, Atsuro Takai, Kazutaka Sonobe. Postsynthetic Defect Formation in Three-Dimensional Hofmann-Type Coordination Polymers and Its Impact on Catalytic Activity. Inorganic Chemistry. 2022, 61 (3), 1697-1703. https://doi.org/10.1021/acs.inorgchem.1c03560

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(abstract)

We report a systematic investigation of post-synthetic defect formation in Hofmann-type coordination polymers M(pz)[M’(CN)4] (M = Fe2+, Co2+, Ni2+; M’ = Pd2+, Pt2+; pz = pyrazine). These compounds readily undergo selective ligand exchange at the pyrazine site when immersed in methanol (MeOH) at ambient temperature. The ligand exchange changes the chemical formula to M(pz)1-x(MeOH)2x[M’(CN)4] (0 < x < 1), affording defective coordination environment around the M ions. The defect concentration is highly dependent on the combination of the metal ions and solvent species, reaching the defect concentration of ca. 30% (x ~ 0.3) at maximum. The magnetic state of one such coordination polymer gives an additional control of the defect formation, making the compound less susceptible to the ligand exchange at the low-spin state. Structures that form the defects at high concentration function as catalysts and promote an acetalization reaction heterogeneously by providing Lewis acidic sites. The solvent-dependent character of the defect formation can be used to control the catalytic activity of the active compounds, demonstrating a facile defect engineering for functionalizing solid materials.

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  • In Copyright

    This document is the Accepted Manuscript version of a Published Article that appeared in final form in norganic Chemistry, copyright © 2022 American Chemical Society. To access the final published article, see ACS Articles on Request.

Keyword: Ligand exchange, Defects, Catalysis, Hofmann-Type Coordination Polymers

Date published: 2022-01-24

Publisher: American Chemical Society (ACS)

Journal:

  • Inorganic Chemistry (ISSN: 1520510X) vol. 61 issue. 3 p. 1697-1703

Funding:

  • Japan Society for the Promotion of Science JP19K21139
  • Japan Society for the Promotion of Science JP20K15306

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.6146

First published URL: https://doi.org/10.1021/acs.inorgchem.1c03560

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Updated at: 2026-01-19 17:07:23 +0900

Published on MDR: 2026-01-20 08:22:14 +0900

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