One-Step and Two-Step Spin-Crossover Iron(II) Complexes of ((2-Methylimidazol-4-yl)methylidene)histamine

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• 作者：Tetsuya Sato ; Koshiro Nishi ; Seiichiro Iijima ; Masaaki Kojima ; Naohide Matsumoto
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：August 3, 2009
• 年：2009
• 卷：48
• 期：15
• 页码：7211-7229
• 全文大小：1470K
• 年卷期：v.48,no.15(August 3, 2009)
• ISSN：1520-510X

文摘

A tridentate ligand ((2-methylimidazol-4-yl)methylidene)histamine (abbreviated as H₂L^2-Me), that is, the 1:1 condensation product of 2-methyl-4-formylimidazole and histamine, was used for the syntheses of a new family of iron(II) spin-crossover (SCO) complexes with the general chemical formulas [Fe(H₂L^2-Me)₂]X₂·solvent (X = Cl, ClO₄, and BPh₄; solvent = 2-PrOH and CH₃CN) and [Fe(H₂L^2-Me)₂]X·Y·solvent (X = Cl and Br; Y = ClO₄, BF₄, PF₆, and AsF₆; solvent = EtOH and 2-PrOH). The complex cation [Fe(H₂L^2-Me)₂]²⁺ is a chiral species due to an octahedral coordination of two unsymmetrical tridentate ligands, has a ligand field strength around the spin-crossover point, and is hydrogen-bonded to anions to form a variety of network structures. The dichloride complexes [Fe(H₂L^2-Me)₂]Cl₂·2-PrOH·0.5H₂O (1) and [Fe(H₂L^2-Me)₂]Cl₂·2-PrOH·H₂O (1′) have a one-dimensional (1D) structure, in which adjacent two chiral complex-cations are doubly bridged by two Cl⁻ ions through NH(histamine)···Cl⁻···HN(2-methyl-4-formylimidazole) hydrogen bonds to give a chiral 1D rod. The chiral rods with the same chirality are stacked in the crystal lattices to give a conglomerate, 1, and those with the opposite chiralities are stacked to give a racemic compound, 1′. The enantiomeric circular dichromism spectra of 1 gave definitive evidence of the conglomerate. Compound 1 showed a two-step SCO, while the desolvated sample showed a steep one-step SCO at T_1/2 = 180 K. A series of complexes, [Fe(H₂L^2-Me)₂]Cl·X·EtOH (X = ClO₄ (2a), BF₄ (2b), PF₆ (2c), and AsF₆ (2d)), [Fe(H₂L^2-Me)₂]Cl·ClO₄·0.5(1-PrOH)·1.5H₂O (2a′), and [Fe(H₂L^2-Me)₂]Br·ClO₄·0.5EtOH (2a′′), display an isomorphous two-dimensional (2D) network at room temperature (296 K), in which the structure is constructed by the NH···Cl⁻ (or Br⁻) hydrogen bonds between the imidazole NH groups of [Fe(H₂L^2-Me)₂]²⁺ and the Cl⁻ (or Br⁻) ion as a connector. The complexes showed a variety of SCO properties depending on the anion, solvent molecule, and the kind of bridging halogen ion. The complexes of ClO₄⁻ (2a, 2a′, 2a′′) and BF₄⁻ (2b) with smaller anions showed a two-step SCO with a wide temperature region of the intermediate state of (high-spin (HS) + low-spin (LS))/2 state, their values of (T_1/2,1, T_1/2,2) being (75, 255 K), (100, 220 K), (110, 220 K), and (100, 260 K), respectively, where the crystal changes from monoclinic P2₁/n in the HS state to triclinic P in the intermediate state. The complexes of PF₆⁻ (2c) and AsF₆⁻ (2d) with larger anions showed a one-step SCO at T_1/2 = 198 and 173 K, respectively, in which the crystal system and space group showed no change during the spin transition. The crystal solvent and halide ion also affected the completeness of the SCO in the lower-temperature region and the steepness of the SCO profile. The experimental results were correlated to the theoretical results based on an Ising-like model. [Fe(H₂L^2-Me)₂](BPh₄)₂·CH₃CN (3) has no network structure. [Fe(H₂L^2-Me)₂](ClO₄)₂ (4) assumes a chiral 3D network structure constructed by the hydrogen bonds between the imidazole groups of one enantiomorph [Fe(H₂L^2-Me)₂]²⁺ and the bridging ClO₄⁻ ion. Compounds 3 and 4 in the solid states are in the HS state, demonstrating that the formation of imidazole−Cl⁻ or Br−hydrogen bonds can give SCO properties, but the hydrogen bond of imidazole−ClO₄⁻ cannot give SCO.