Polymorphs of spin-crossover iron(II) complex fac-[FeII(HLn-Pr)3]Cl.PF6 (HLn-pr=2-methylimidazol-4-yl-methylideneamino-n-propyl): Assembly structures and scan rate dependent spin-crossover properties with thermal hysteresis

被引:9
作者
Ueno, Takahiro [1 ]
Ii, Yuto [1 ]
Fujinami, Takeshi [1 ]
Matsumoto, Naohide [1 ]
Iijima, Seiichiro [2 ]
Sunatsuki, Yukinari [3 ]
机构
[1] Kumamoto Univ, Dept Chem, Fac Sci, Kurokami 2-39-1, Kumamoto 8608555, Japan
[2] Natl Inst Adv Ind Sci & Technol, Tsukuba, Ibaraki 3058566, Japan
[3] Okayama Univ, Dept Chem, Fac Sci, Tsushima Naka 3-1-1, Okayama 7008530, Japan
基金
日本学术振兴会;
关键词
Iron(II) complex; Bidentate ligand; Hydrogen bond; Spin crossover; 2D network structure; TRIPODAL IMIDAZOLE COMPLEXES; HYDROGEN-BONDS; INTERMEDIATE PHASE; TRANSITION; COMPOUND; CHLORIDE; DICHLORIDE; BEHAVIORS; DYNAMICS; VARIETY;
D O I
10.1016/j.poly.2017.03.028
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Two polymorphs of iron(II) complex fac-[Fe-II(HLn-Pr)(3)]Cl.PF6, 1 and 2, were obtained (HLn-Pr = 2-methylimidazole-4-yl-methylideneamino-n-propyl ligand). Complex cations, fac-[Fe-II(HLn-Pr)(3)](2+), of 1 and 2 had similar octahedral and facial geometries coordinated with three bidentate HLn-Pr ligands. The three imidazole groups in fac-[Fe-II(HLn-Pr)(3)](2+) with Delta- and Lambda-enantiomorphs are hydrogen-bonded with three Cl- ions, forming one-dimensional (1D) and two-dimensional (2D) network structures in 1 and 2, respectively. Complex 1 had a ladder-like 1D structure formed by imidazole...chloride hydrogen bonds, with a circular binuclear net unit of {...fac-[Fe-II(HLn-Pr)(3)](2+)...Cl-...}(2), and showed two successive scan rate dependent spin crossover (SCO) processes with thermal hysteresis. Complex 2 had a 2D network structure formed by imidazole...chloride hydrogen bonds with circular binuclear and tetranuclear net units of {...fac-[Fe-II(HLn-Pr)(3)](2+)...Cl-...}(2),(4), and showed a one-step scan rate dependent SCO profile centered at 143 K with thermal hysteresis. The relaxation property was identified from the scan rate dependence of magnetic susceptibility and temperature dependent Mossbauer spectra and X-ray diffraction studies. The crystal structure of 2 was analyzed at 12 temperatures in a cooling cycle. Upon lowering the temperature, the crystal system transformed from a monoclinic to a triclinic lattice at 210 K in a high-spin state, and then transformed to a low-spin state at 150 K in the triclinic system. (c) 2017 Elsevier Ltd. All rights reserved.
引用
收藏
页码:13 / 22
页数:10
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