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
1. [1]
  [1] Halcrow M A. Chem. Soc. Rev., 2011,40:4119-4142
2. [2]
  [2] Gütlich P, Hauser A, Spiering H. Angew. Chem. Int. Ed., 1994,33:2024-2054
3. [3]
  [3] Guionneau P. Dalton Trans., 2014,43:382-393
4. [4]
  [4] Tian H, Feng Y L. J. Mater. Chem., 2008,18:1617-1622
5. [5]
  [5] Ferrere S, Gregg B A. J. Am. Chem. Soc., 1998,120:843-844
6. [6]
  [6] Bousseksou A, Molnár G, Salmon L, et al. Chem. Soc. Rev., 2011,40:3313-3335
7. [7]
  [7] Verdejo B, Gil-Ramirez G, Ballester P. J. Am. Chem. Soc., 2009,131:3178-3179
8. [8]
  [8] Matouzenko G S, Jeanneau E, Verat A Y, et al. Dalton Trans., 2011,40:9608-9618
9. [9]
  [9] Takahashi O, Kohno Y, Nishio M. Chem. Rev., 2010,110: 6049-6076
10. [10]
  [10] Nihei M, Takahashi N, Nishikawa H, et al. Dalton Trans., 2011,40:2154-2156
11. [11]
  [11] Faulmann C, Jacob K, Dorbes S, et al. Inorg. Chem., 2007,46:8548-8559
12. [12]
  [12] Gaspar A B, Seredyuk M, Güetlich P. Coord. Chem. Rev., 2009,253:2399-2413
13. [13]
  [13] Hayami S, Danjobara K, Inoue K, et al. Adv. Mater., 2004, 16:869-872
14. [14]
  [14] Nihei M, Sekine Y, Suganami N, et al. J. Am. Chem. Soc., 2011,133:3592-3600
15. [15]
  [15] (a)Salmon L, Molnar G, Zitouni D, et al. J. Mater. Chem., 2010,20:5499-5503
16. [16]
  (b)Gaspar A B, Ksenofontov V, Seredyuk M, et al. Coord. Chem. Rev., 2005,249:2661-2676
17. [17]
  (c)Lacroix P G, Malfant I, Real J A, et al. Eur. J. Inorg. Chem., 2013,615-627
18. [18]
  [16] Rikken G L J A, Raupach E. Nature, 1997,390:493-494
19. [19]
  [17] Barron L D. Nature, 2000,405:895-896
20. [20]
  [18] (a)Marcelo C, Sara G F, Ramon G M J. Adv. Mater., 2012, 24:3120-3123
21. [21]
  (b)Cai H L, Zhang Y, Fu D W, et al. J. Am. Chem. Soc., 2012,134:18487-18490
22. [22]
  (c)Xu G C, Zhang W, Ma X M, et al. J. Am. Chem. Soc., 2011,133:14948-14951
23. [23]
  [19] Train C, Gheorghe R, Krstic V, et al. Nat. Mater., 2008,7: 729-734
24. [24]
  [20] (a)Fu D W, Zhang W, Cai H L, et al. Angew. Chem. Int. Ed., 2011,50:11947-11951
25. [25]
  (b)Liu C M, Xiong R G, Zhang D Q, et al. J. Am. Chem. Soc., 2010,132:4044-4045
26. [26]
  (c)Cui H B, Wang Z M, Takahashi K, et al. J. Am. Chem. Soc., 2006,128:15074-15075
27. [27]
  (d)Ohkoshi S I, Tokoro H, Matsuda T, et al. Angew. Chem. Int. Ed., 2007,3302-3305
28. [28]
  [21] SAINT-Plus, Version 6.02, Bruker Analytical X-ray System, Madison, WI, 1999.
29. [29]
  [22] Sheldrick G M. SADABS An Empirical Absorption Correction Program, Bruker Analytical X-ray Systems, Madison, WI, 1996.
30. [30]
  [23] Sheldrick G M. SHELXTL-97, University of Göttingen, Germany, 1997.
31. [31]
  [24] Ulrich K, Alex V Z. Angew. Chem. Int. Ed., 1999,38: 302-322
32. [32]
  [25] Nishida Y, Kino K, Kida S. Dalton Trans., 1987,5:1157 -1161
33. [33]
  [26] Koenig E. Prog. Inorg. Chem., 1987,35:527-623
34. [34]
  [27] Vankó G, Glatzel P, Pham V T, et al. Angew. Chem. Int. Ed., 2010,49:5910-5912
35. [35]
  [28] Niel V, Martinez-Agudo J M, Muñoz M C. Inorg. Chem., 2001,40:3838-3839
36. [36]
  [29] Yamada M, Hagiwara H, Torigoe H. Eur. J. Inorg. Chem., 2006,12:4536-4549
37. [37]
  [30] Nishi K, Matsumoto N, Iijima S. Inorg. Chem., 2011,50: 11303-11305
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