Citation: WANG Ya-Qin, ZHANG Hai-Xia, ZHANG Shu-Heng, HE Wei, GE Fang-Yuan, CHEN Yu-Xin, GU Zhi-Guo. Synthesis and Gelation Ability of Spin-Crossover Iron(Ⅱ) Alkyl Imidazole Complexes[J]. Chinese Journal of Inorganic Chemistry, ;2019, 35(12): 2260-2268. doi: 10.11862/CJIC.2019.254 shu

Synthesis and Gelation Ability of Spin-Crossover Iron(Ⅱ) Alkyl Imidazole Complexes

1.
School of Chemistry and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China
2.
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, Wuxi, Jiangsu 214122, China

Corresponding author: GU Zhi-Guo, zhiguogu@jiangnan.edu.cn
Received Date: 5 June 2019
Revised Date: 1 August 2019

Figures(7)

Complexes 1~5 were synthesized by one-step reaction of 1-heptyl-1H-imidazole-2-carboxaldehyde(L¹), 1-tetradecyl-1H-imidazole-2-carbaldehyde(L²), 1-hexadecyl-1H-imidazole-2-carbaldehyde(L³), 1-octadecyl-1H-imidazole-2-carboxaldehyde(L⁴), 1-eicosyl-1H-imidazole-2-carboxaldehyde(L⁵) with ferrous tetrafluoroborate and 1-phenylethylamine, respectively. The five complexes have been determined by IR spectra and elemental analysis. X-ray crystallography reveals that each unit in 1 contains one[Fe(L¹)₃]²⁺ cation and two BF₄^- anions. The iron(Ⅱ) center coordinates with six N donor atoms from three ligands to form a octahedral mononuclear compound with fac-configuration. The Fe(Ⅱ)-N bond distances indicate that the Fe(Ⅱ) sites of 1 are in low-spin state. As for[Fe(L¹)₃]²⁺, intramolecular π-π interactions are present between phenyl group and imidazole ring of an adjacent ligand, and then a supramolecular architectures are further formed by C-H…π interactions between alkyl chain and aromatic ring. Magnetic measurements reveal that 1 displays incomplete spin-crossover behaviour at 341 K, and 2 is a high-spin paramagnetic compound, while 3~5 show incomplete spin-crossover behaviour. The corresponding metallogels MOG2~MOG5 were formed by using complexes 2~5 with longer alkyl chains as gelator and cyclohexane as solvent. Scanning electron microscopy(SEM) images showed that the MOG2~MOG5 had 3D network pore structure. Reversible gel-sol transitions were found in MOG2~MOG5. Under the influence of heat and mechanical force, MOG2~MOG5 were rapidly converted to sol, which can be restored to gel after being stationary, showing good stimulation-response and self-healing ability.
- Fe(Ⅱ) complexes,
- spin-crossover,
- metallogels,
- stimulus responsiveness
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沈阳化工大学材料科学与工程学院沈阳 110142