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Four bimetallic ammonium formate frameworks: structures, magnetism and dielectricity

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Abstract

The synthesis, crystal structures, magnetic and dielectric properties of four ammonium bimetallic formate frameworks [AI][GaIIICoII(HCOO)6] for AI = CH3NH3+ (1), (CH3)2NH2+ (2), CH3CH2NH3+ (3) and (CH3CH2)2NH2+ (4) have been reported. They are isomorphic and crystallize in the trigonal P\(\bar{3}\)1c space group at both 110 and 293 K. The structures possess [GaIIICoII(HCOO)6]− anionic metal formate frameworks of binodal (412·63)(49·66) topology, in which the disordered ammonium cations are located in the cavities. The magnetic data of complex 2 was fitted by the one-ion approximation for CoII ion with spin–orbit coupling in Oh symmetry giving λ = − 102.7 cm−1. The dielectric studies of 1 and 2 showed that the dielectric abnormality was caused by the weakening of the movement of the ammonium cations with the decrease in temperature. The activation energies for the motions of ammonium cations in 1 and 2 were determined to be 3.00 and 3.19 × 103 K, respectively.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21771111, 21101096, and 21371104) and the Hebei Province 2020 Overseas Student Introduction Program (No. C20200317).

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Authors and Affiliations

  1. Tianjin Key Laboratory of Chemical Process Safety, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, 300130, People’s Republic of China

    Shuo-Wen Wang, Dian Chen & Chun Yang

  2. College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071, People’s Republic of China

    Kai Wang & Qing-Lun Wang

Authors
  1. Shuo-Wen Wang
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  2. Kai Wang
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  3. Dian Chen
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  4. Chun Yang
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  5. Qing-Lun Wang
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Correspondence to Chun Yang or Qing-Lun Wang.

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Supplementary Information

Crystallographic data (excluding structure factors) for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication Nos. CCDC 2019804-2019811 for 1–4. Copies of the data can be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge CB21EZ, UK (Fax: +44-1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).

The online version contains supplementary material (Table S1 and S2, Fig. S1 – S3) are available at https://doi.org/10.1007.

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Supplementary file1 (DOCX 250 kb)

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Wang, SW., Wang, K., Chen, D. et al. Four bimetallic ammonium formate frameworks: structures, magnetism and dielectricity. Transit Met Chem 47, 183–188 (2022). https://doi.org/10.1007/s11243-022-00502-x

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  • DOI: https://doi.org/10.1007/s11243-022-00502-x

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