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Lanthanide-Based Porous Coordination Polymers: Syntheses, Slow Relaxation of Magnetization, and Magnetocaloric Effect

  • Chinmoy Das
    Chinmoy Das
    Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra, India
    More by Chinmoy Das
  • Apoorva Upadhyay
    Apoorva Upadhyay
    Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra, India
  • Kamal Uddin Ansari
    Kamal Uddin Ansari
    Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra, India
  • Naoki Ogiwara
    Naoki Ogiwara
    Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
  • Takashi Kitao
    Takashi Kitao
    Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
  • Satoshi Horike*
    Satoshi Horike
    Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
    Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Institute for Advanced Study, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
    AIST-Kyoto University Chemical Energy Materials Open Innovation Laboratory (ChEM-OIL), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
    *E-mail for S.H.: [email protected]
  • , and 
  • Maheswaran Shanmugam*
    Maheswaran Shanmugam
    Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra, India
    *E-mail for M.S.: [email protected]
Cite this: Inorg. Chem. 2018, 57, 11, 6584–6598
Publication Date (Web):May 16, 2018
Copyright © 2018 American Chemical Society

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    Abstract Image

    Two lanthanide-containing structurally analogous porous coordination polymers (PCPs) have been isolated with the general molecular formula [Ln2(L1)2(H2O)4(ox)]n.4nH2O (where L1 = fumarate, ox = oxalate; Ln = Dy (1), Gd (2)). Thermogravimetric analysis (TGA) and TG-MS measurements performed on 1 and 2 suggest that not only the solvated water molecules in the crystal lattice but also the four coordinated water molecules on the respective lanthanides in 1 and 2 are removed upon activation. Due to the removal of the waters, 1 and 2 lost their crystallinity and became amorphous, as confirmed by powder X-ray diffraction (PXRD). We propose the molecular formula [Ln2(L1)2(ox)]n for the amorphous phase of 1 and 2 (where Ln = Dy (1′), Gd (2′)) on the basis of XANES, EXAFS, and other experimental investigations. Magnetization relaxation dynamics probed on 1 and 1′ reveal two different relaxation processes with effective energy barriers of 53.5 and 7.0 cm–1 for 1 and 45.1 and 6.4 cm–1 for 1′, which have been rationalized by detailed ab initio calculations. For the isotropic lanthanide complexes 2 and 2′, magnetocaloric effect (MCE) efficiency was estimated through detailed magnetization measurements. We have estimated −ΔSm values of 52.48 and 41.62 J kg1– K–1 for 2′ and 2, respectively, which are one of the largest values reported for an extended structure. In addition, a 26% increase in −ΔSm value in 2′ in comparison to 2 is achieved by simply removing the passively contributing (for MCE) solvated water molecule in the lattice and coordinated water molecules.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00720.

    • Crystallographic parameters, TGA analysis, TG-MS data, supporting dc and ac magnetic data, computed crystal field parameters, and energies of the computed KDs of SINGLE_ANISO and POLY_ANISO (PDF)

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    CCDC 1830577 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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