Citation: REN Dong-Hong, LIU Zhi-Ming, SUN Xiao-Li, GU Ling, QIU Dan, GU Zhi-Guo, LI Zai-Jun. Syntheses, Structures and Magnetic Properties of Homochiral Spin-Crossover Iron(Ⅱ) Schiff-Base Complexes[J]. Chinese Journal of Inorganic Chemistry, ;2015, (3): 536-542. doi: 10.11862/CJIC.2015.040 shu

Syntheses, Structures and Magnetic Properties of Homochiral Spin-Crossover Iron(Ⅱ) Schiff-Base Complexes

REN Dong-Hong ¹ ,
LIU Zhi-Ming ¹ ,
SUN Xiao-Li ¹ ,
GU Ling ¹ ,
QIU Dan ¹ ,
GU Zhi-Guo ^1,2,, ,
LI Zai-Jun ¹

1.
1 School of Chemistry and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China;
2.
2 The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, Wuxi, Jiangsu 214122, China

Corresponding author: GU Zhi-Guo,
Received Date: 17 October 2014
Available Online: 10 November 2014
Fund Project: 国家自然科学基金(No.21101078, 21276105) (No.21101078, 21276105)新世纪优秀人才计划(No.NCET-11-0657) (No.NCET-11-0657) 江苏省自然科学基金(No.BK2011143)资助。 (No.BK2011143)

Two homochiral mononuclear spin-crossover iron(Ⅱ) complexes, namely, fac-Λ-[Fe(R-L₁)₃](ClO₄)₂ (1), fac-Λ-[Fe(R-L₂)₃](ClO₄)₂ (2) have been successfully synthesized by subcomponent self-assembly of Fe(ClO₄)2, 4-(imidazole-2-carboxaldehyde)butyronitrile and optical phenylethylamine derivatives. The two complexes have been determined by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra, ¹H NMR spectra, UV spectra and CD spectra. X-ray crystallography revealed that the iron(Ⅱ) center in 1 and 2 assumed an octahedral coordination environment with six N donor atoms from three unsymmetrical bidentate chiral schiff-base ligands. Each unit contained one [Fe(L)₃]²⁺ cation and two ClO₄^- anions. [Fe(L)₃]₂ components were chiral with Λ configuration due to the screw coordination arrangement of the chiral ligand around Fe(Ⅱ) centers. The Fe(Ⅱ)-N bond distances indicated that the Fe(Ⅱ) sites of 1 and 2 were in low-spin state. As for [Fe(L)₃]²⁺, intramolecular π-π interactions were present between phenyl group and imidazole ring of an adjacent ligand. In 1 and 2, 3D supramolecular architectures were formed through intermolecular C-H…π interactions. Circular dichromism spectra confirmed the presence of non-racemic chiral metal centers in solution for complexes 1 and 2. Magnetic measurements revealed that 1 and 2 displayed obviously spin-crossover behaviour at 232 and 250 K, respectively. Complexes 1 and 2 crystallized in the same chiral space group with similar packing modes and intermolecular interactions, therefore their different SCO bahaviors mainly resulted from substitution effect.
- homochiral;spin-crossover;iron(Ⅱ) complexes;schiff-base
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