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High-temperature Spin Crossover of a Solvent-Free Iron(II) Complex with the Linear Hexadentate Ligand [Fe(L2-3-2Ph)](AsF6)2 (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine)

Department of Chemistry, Faculty of Education, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan
Magnetochemistry 2019, 5(1), 10; https://doi.org/10.3390/magnetochemistry5010010
Received: 29 December 2018 / Revised: 18 January 2019 / Accepted: 20 January 2019 / Published: 1 February 2019
(This article belongs to the Special Issue Coordination Compounds for Coordination Molecule-Based Devices)
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Abstract

A novel mononuclear iron(II) complex with a linear hexadentate N6 ligand, containing two 1,2,3-triazole moieties, [Fe(L2-3-2Ph)](AsF6)2 (1), was synthesized (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine). Variable-temperature magnetic susceptibility measurements revealed a gradual one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states above room temperature (T1/2 = 468 K). The spin transition was further confirmed by differential scanning calorimetry (DSC). A single-crystal X-ray diffraction study showed that the complex was in the LS state (S = 0) at room temperature (296 K). In the crystal lattice, a three-dimensional (3D) supramolecular network was formed by intermolecular CH⋯π and π–π interactions of neighboring complex cations [Fe(L2-3-2Ph)]2+. AsF6 ions were located interstitially in the 3D network of complex cations, with no solvent-accessible voids. The crystal structure at 448 K (mixture of HS and LS species) was also successfully determined thanks to the thermal stability of the solvent-free crystal. View Full-Text
Keywords: spin crossover; iron(II); mononuclear; 1,2,3-triazole; linear hexadentate ligand; spin transition; magnetism; calorimetry; crystal structure spin crossover; iron(II); mononuclear; 1,2,3-triazole; linear hexadentate ligand; spin transition; magnetism; calorimetry; crystal structure
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Hagiwara, H. High-temperature Spin Crossover of a Solvent-Free Iron(II) Complex with the Linear Hexadentate Ligand [Fe(L2-3-2Ph)](AsF6)2 (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine). Magnetochemistry 2019, 5, 10.

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