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

https://mdr.nims.go.jp/datasets/b1aa8a3a-ae24-4be9-b392-e1f38193117b

## File

- [Revised manuscript.pdf](https://mdr.nims.go.jp/filesets/dd3eeb19-bde5-4953-a404-a2345b3730ad/download) ([Detail](https://mdr.nims.go.jp/filesets/dd3eeb19-bde5-4953-a404-a2345b3730ad.md))

## Id

b1aa8a3a-ae24-4be9-b392-e1f38193117b

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2026-01-19T07:55:16.217437Z

## Updated at

2026-01-19T08:07:23.801172Z

## Published at

2026-01-19T23:22:14.598711Z

## Doi

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

## First published url

https://doi.org/10.1021/acs.inorgchem.1c03560

## Date published

2022-01-24

## Recorded date published

2022-1-24

## Resource type

journal_article

## Manuscript type

accepted_manuscript

## Collection



## Title

- title: Postsynthetic Defect Formation in Three-Dimensional Hofmann-Type Coordination
    Polymers and Its Impact on Catalytic Activity
  title_type: original
  lang: en

## Description

- description: 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.
  description_type: abstract
  lang: und

## Creator

- name: Daiki Umeyama
  role: author
  orcid: https://orcid.org/0000-0003-4773-4020
  organization: National Institute for Materials Science
- name: Atsuro Takai
  role: author
  orcid: https://orcid.org/0000-0003-3457-3352
  organization: National Institute for Materials Science
- name: Kazutaka Sonobe
  role: author

## Contact agent



## Publisher

organization: American Chemical Society (ACS)

## Managing organization



## Keyword

- subject: Ligand exchange
  schema: not_defined
- subject: Defects
  schema: not_defined
- subject: Catalysis
  schema: not_defined
- subject: Hofmann-Type Coordination Polymers
  schema: not_defined

## Rights

- description: 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.
  identifier: http://rightsstatements.org/vocab/InC/1.0/

## Other identifier(s)



## Data origin

- data_origin_type: other

## Embargo

start_date: 2022-01-09
end_date: 2023-01-09

## Journal

- title: Inorganic Chemistry
  issn: 1520510X
  volume: '61'
  issue: '3'
  start_page: 1697
  end_page: 1703

## Conference



## Related item



## Funding

- identifier: JP19K21139
  funder_name: Japan Society for the Promotion of Science
- identifier: JP20K15306
  funder_name: Japan Society for the Promotion of Science

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## Fileset

- id: dd3eeb19-bde5-4953-a404-a2345b3730ad
  filename: Revised manuscript.pdf
  content_type: application/pdf
  size: 961953
  md5: d126b6299b7e5ed4b028146df64f54a2

## Thumbnail

fileset_id: dd3eeb19-bde5-4953-a404-a2345b3730ad
filename: Revised manuscript.pdf