Syntheses, Structures, and Magnetic Properties of a Novel mer-[(bbp)FeIII(CN)3]2鈥?/sup> Building Block (bbp: bis(2-benzimidazolyl)pyridine dianion) and Its Related He

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• 作者：Anangamohan Panja ; Philippe Guionneau ; Ie-Rang Jeon ; Stephen M. Holmes ; Rodolphe Cl茅rac ; Corine Mathoni猫re
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：November 19, 2012
• 年：2012
• 卷：51
• 期：22
• 页码：12350-12359
• 全文大小：468K
• 年卷期：v.51,no.22(November 19, 2012)
• ISSN：1520-510X

文摘

A new symmetrical tricyanide building block mer-[Fe(bbp)(CN)₃]^{2鈥?/sup> [1; bbp = bis(2-benzimidazolyl)pyridine dianion] has been prepared and structurally and magnetically characterized. It forms a new low-spin meridionally capped {FeIIIL(CN)₃} fragment with the tridentate bbp ligand. The reaction of 1 with NiII salts in the presence of various ancillary ligands affords several new cyanido-bridged complexes: a trinuclear complex {[Ni(ntb)(MeOH)]₂[Fe(bbp)(CN)₃][ClO₄]₂}路2MeOH (2), a tetranuclear compound {[Ni(tren)]₂[Fe(bbp)(CN)₃]₂}路7MeOH (3), and a one-dimensional heterobimetallic system: {[Ni(dpd)₂]₂[Fe(bbp)(CN)₃]₂}路9MeOH路3H₂O (4) [ntb = tris(2-benzimidazolylmethyl)amine, tren = tris(2-aminoethyl)amine, and dpd = 2,2-dimethyl-1,3-propanediamine]. The structural data shows that 2 is a linear complex in which a central FeIII ion links two adjacent NiII ions via axial cyanides, while 3 is a molecular square that contains cyanido-bridged NiII and FeIII ions at alternate corners. Complex 4 is a one-dimensional system that is composed of alternating cyanido-bridged NiII and FeIII centers. Compounds 2鈥?b>4 display extensive hydrogen bonding and moderately strong 蟺鈥撓€ stacking interactions in the solid state. Magnetic studies show that ferromagnetic exchange is operative within the FeIII_LS(渭-CN)NiII units of 2鈥?b>4.}