Citation: GU Ling, REN Dong-Hong, LIU Zhi-Ming, SUN Xiao-Li, QIU Dan, GU Zhi-Guo, . Two Homochiral Spin-Crossover Iron(Ⅱ) Complexes Based on Bidentate Imidazole Schiff Base Ligands[J]. Chinese Journal of Inorganic Chemistry, ;2015, 31(7): 1357-1364. doi: 10.11862/CJIC.2015.183 shu

Two Homochiral Spin-Crossover Iron(Ⅱ) Complexes Based on Bidentate Imidazole Schiff Base Ligands

GU Ling ¹ ,
REN Dong-Hong ¹ ,
LIU Zhi-Ming ¹ ,
SUN Xiao-Li ¹ ,
QIU Dan ¹ ,
GU Zhi-Guo ^1,2,, ,
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, Wuxi, Jiangsu 214122, China

Corresponding author: GU Zhi-Guo, ,
Received Date: 4 March 2015
Available Online: 8 May 2015
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)

Based on the bidentate schiff base ligands involving phenyl and imidazole groups, two homochiral mononuclear spin-crossover iron(Ⅱ) complexes, fac-Δ-[Fe(S-L₁)₃][ClO₄]₂ (1), mer-Λ-[Fe(R-L₂)₃][ClO₄]₂·Et₂O (2) (L₁=1-parachlorophenyl-N-(1-n-propylenyl-1H-imidazol-2-ylmethylene)ethanamine; L₂=1-phenyl-N-(1-iso-butenyl-1H-imidazol-2-ylmethylene)ethanamine) have been synthesized. 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 6 N donor atoms from three unsymmetrical bidentate chiral schiff base ligands. Each unit contained one [Fe(L_n)₃]²⁺ cation and two ClO₄^- anions in 1. While 2 contained two [Fe(L_n)₃]²⁺ cation, four ClO₄^- anions and one diethyl ether molecular. [Fe(L_n)₃]²⁺ components were chiral with single 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 were in low-spin state, while the Fe(Ⅱ) centers of 2 were in high-spin state. As for [Fe(L_n)₃]²⁺, intramolecular π-π interactions were present between phenyl group and imidazole ring of an adjacent ligand. In 1 and 2, supramolecular architectures were formed through intermolecular C-H…π and/or C-Cl…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 372 K and 146 K, respectively. Complexes 1 and 2 crystallized in different packing modes and intermolecular interactions, therefore their SCO bahaviors were different.
- homochiral;spin-crossover;iron(Ⅱ) complexes;schiff base
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