Abstract
With adequate building blocks, metal–organic frameworks (MOFs) can combine magnetic ordering and porosity. This makes MOFs a promising platform for the development of stimuli-responsive materials that show drastically different magnetic properties depending on the presence or absence of guest molecules within their pores. Here we report a CO2-responsive magnetic MOF that converts from ferrimagnetic to paramagnetic on CO2 adsorption, and returns to the ferrimagnetic state on CO2 desorption. The ferrimagnetic material is a layered MOF with a [D+–A−–D] formula, produced from the reaction of trifluorobenzoate-bridged paddlewheel-type diruthenium(ii) clusters as the electron donor (D) with diethoxytetracyanoquinodimethane as the electron acceptor (A). On CO2 uptake, it undergoes an in-plane electron transfer and a structural transition to adopt a [D–A–D] paramagnetic form. This magnetic phase change, and the accompanying modifications to the electronic conductivity and permittivity of the MOF, are electronically stabilized by the guest CO2 molecules accommodated in the framework.
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Data availability
The data that support this work are available in the article and its Supplementary Information files. Further raw data are available from the corresponding authors upon reasonable request. X-ray crystallographic data have been deposited as CIFs at the Cambridge Crystallographic Data Centre (http://www.ccdc.cam.ac.uk/) with CCDC numbers 1914693 (1-DCM), 1914694 (1), 1914695 (1⊃CO2-I) and 1914696 (1⊃CO2-II). A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.
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Acknowledgements
We thank H. Sato for his assistance with the single-crystal X-ray crystallography of the CO2-accommodated compounds. This work was supported by a Grant‐in‐Aid for Scientific Research (nos 16H02269, 18K19050, 18K05055, 18H05208, 19K05401, 20K15294 and 20H00381) from MEXT, Japan, and on Innovative Areas (‘π‐System Figuration’ Area 2601, no. 17H05137) from JSPS, Japan, the GIMRT programme, the E‐IMR project and a Grant Fund for Research and Education (no. J190001232). J.Z. is thankful for the JSPS KAKENHI (No. 17J02497).
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J.Z. and H.M. formulated the project. J.Z. performed the experiments. W.K. established the experimental set-ups, especially the measurements with the gases, and supported the experiments. Y.K. performed the theoretical calculations. All the authors contributed to the writing of the manuscript.
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Supplementary Information
Supplementary Figs. 1–43, discussion and Tables 1–8 (except Table 6 as separate file).
Supplementary Table 6
Atomic coordinates for Models A–D.
Supplementary Data
Cif for 1-DCM
Supplementary Data
Cif for 1
Supplementary Data
Cif for 1-CO2-I
Supplementary Data
Cif for 1-CO2-II
Source data
Source Data Fig. 1
Source data for Fig. 1f,1g.
Source Data Fig. 2
Source data for Fig. 2a–f.
Source Data Fig. 4
Source data for Fig. 4a–g.
Source Data Fig. 5
Source data for Fig. 5a–c.
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Zhang, J., Kosaka, W., Kitagawa, Y. et al. A metal–organic framework that exhibits CO2-induced transitions between paramagnetism and ferrimagnetism. Nat. Chem. 13, 191–199 (2021). https://doi.org/10.1038/s41557-020-00577-y
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DOI: https://doi.org/10.1038/s41557-020-00577-y
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