Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal
In this study, we comparatively analyzed the variable-temperature crystal structures for two isomorphous salts, [1-benzyl-4-aminopyridinium][M(mnt)<sub>2</sub>] (M = Ni or Cu; mnt<sup>2−</sup> = maleonitriledithiolate; labeled as <b>APy-Ni</b> or <b>APy-Cu&l...
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2025-01-01
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| author | Yin Qian Yan Gao Lei Xu Reinhard K. Kremer Jin Zhang Xiao-Ming Ren |
| author_facet | Yin Qian Yan Gao Lei Xu Reinhard K. Kremer Jin Zhang Xiao-Ming Ren |
| author_sort | Yin Qian |
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| description | In this study, we comparatively analyzed the variable-temperature crystal structures for two isomorphous salts, [1-benzyl-4-aminopyridinium][M(mnt)<sub>2</sub>] (M = Ni or Cu; mnt<sup>2−</sup> = maleonitriledithiolate; labeled as <b>APy-Ni</b> or <b>APy-Cu</b>). Both salts crystallize in the triclinic <i>P</i>–1 space group at 296 K, comprising linear [M(mnt)<sub>2</sub>]<sup>−</sup> (M = Ni or Cu) tetramers. A magnetostructural phase transition occurs at T<sub>C</sub>~190 K in S = ½ <b>APy-Ni</b> at ambient pressure, with a conversion of paramagnetic tetramers into nonmagnetic spin-paired dimers. The discontinuous alteration of cell parameters at T<sub>C</sub> signifies the characteristic of first-order phase transition in <b>APy-Ni</b>. No such transition appears in the nonmagnetic <b>APy-Cu</b> within the same temperature vicinity, demonstrating the magnetic interactions promoting the structural phase transition in <b>APy-Ni</b>, which is further reinforced through a comparison of the lattice formation energy between <b>APy-Ni</b> and <b>APy-Cu</b>. The phase transition may bear a resemblance to the mechanisms typically observed in spin-Peierls systems. We further explored the magnetic and phase transition properties of <b>APy-Ni</b> under varying pressures. Significantly, T<sub>C</sub> shows a linear increase with rising pressure within the range of 0.003–0.88 GPa, with a rate of 90 K GPa<sup>−1</sup>, manifesting that the applied pressure promotes the transition from tetramer to dimer. |
| format | Article |
| id | doaj-art-3d297070a86945ec86d86ccd108440c8 |
| institution | DOAJ |
| issn | 2312-7481 |
| language | English |
| publishDate | 2025-01-01 |
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| series | Magnetochemistry |
| spelling | doaj-art-3d297070a86945ec86d86ccd108440c82025-08-20T02:44:42ZengMDPI AGMagnetochemistry2312-74812025-01-01112810.3390/magnetochemistry11020008Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular CrystalYin Qian0Yan Gao1Lei Xu2Reinhard K. Kremer3Jin Zhang4Xiao-Ming Ren5State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaState Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaState Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaMax-Planck-Institute für Festkörperforschung, Heisenbergstrasse 1, 70569 Stuttgart, GermanyState Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaState Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaIn this study, we comparatively analyzed the variable-temperature crystal structures for two isomorphous salts, [1-benzyl-4-aminopyridinium][M(mnt)<sub>2</sub>] (M = Ni or Cu; mnt<sup>2−</sup> = maleonitriledithiolate; labeled as <b>APy-Ni</b> or <b>APy-Cu</b>). Both salts crystallize in the triclinic <i>P</i>–1 space group at 296 K, comprising linear [M(mnt)<sub>2</sub>]<sup>−</sup> (M = Ni or Cu) tetramers. A magnetostructural phase transition occurs at T<sub>C</sub>~190 K in S = ½ <b>APy-Ni</b> at ambient pressure, with a conversion of paramagnetic tetramers into nonmagnetic spin-paired dimers. The discontinuous alteration of cell parameters at T<sub>C</sub> signifies the characteristic of first-order phase transition in <b>APy-Ni</b>. No such transition appears in the nonmagnetic <b>APy-Cu</b> within the same temperature vicinity, demonstrating the magnetic interactions promoting the structural phase transition in <b>APy-Ni</b>, which is further reinforced through a comparison of the lattice formation energy between <b>APy-Ni</b> and <b>APy-Cu</b>. The phase transition may bear a resemblance to the mechanisms typically observed in spin-Peierls systems. We further explored the magnetic and phase transition properties of <b>APy-Ni</b> under varying pressures. Significantly, T<sub>C</sub> shows a linear increase with rising pressure within the range of 0.003–0.88 GPa, with a rate of 90 K GPa<sup>−1</sup>, manifesting that the applied pressure promotes the transition from tetramer to dimer.https://www.mdpi.com/2312-7481/11/2/8metal-bis-dithiolene saltthermotropic phase transitionpiezotropic phase transitionlinear tetramerspin-paired dimer |
| spellingShingle | Yin Qian Yan Gao Lei Xu Reinhard K. Kremer Jin Zhang Xiao-Ming Ren Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal Magnetochemistry metal-bis-dithiolene salt thermotropic phase transition piezotropic phase transition linear tetramer spin-paired dimer |
| title | Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal |
| title_full | Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal |
| title_fullStr | Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal |
| title_full_unstemmed | Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal |
| title_short | Comprehensively Understanding the Transformation of Paramagnetic Tetramer to Spin-Paired Dimer in an S = ½ Molecular Crystal |
| title_sort | comprehensively understanding the transformation of paramagnetic tetramer to spin paired dimer in an s 1 2 molecular crystal |
| topic | metal-bis-dithiolene salt thermotropic phase transition piezotropic phase transition linear tetramer spin-paired dimer |
| url | https://www.mdpi.com/2312-7481/11/2/8 |
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