Hexanuclear iron(III) alpha-aminophosphonate: synthesis, structure, and magnetic properties of a molecular wheel

Doroshenko Iaroslav; Babiak Michal; Buchholz Axel; Tucek Jiri; Plass Winfried; Pinkas Jiri

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Hexanuclear iron(III) alpha-aminophosphonate: synthesis, structure, and magnetic properties of a molecular wheel

机译：六核铁（III）α-氨基磷酸酯：分子轮的合成，结构和磁性

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A new hexanuclear molecular iron phosphonate complex, [Fe-6(HAIPA)(12)(OH)(6)]center dot nH(2)O (1 center dot n(2)O) (H(2)AIPA = NH2(CH3)(2)CP(O)(OH)(2), (2-aminopropan-2-yl) phosphonic acid), was synthesized from Fe2+ and Fe3+ salts in water by interaction with the ligand salts. Addition of corresponding amounts of sodium or tetramethylammonium salts of H2AIPA to the solution of iron precursors led to the formation of large bright-green crystals of complex 1. Isolated products were studied by spectroscopic and analytical methods -IR, Mossbauer spectroscopy, TG/DSC, ICP-OES, and CHN analysis. A novel {Fe-6} hexanuclear molecular structure of 1 was confirmed by single crystal X-ray diffraction analysis. An octahedral coordination environment of iron cations is formed by phosphonate and hydroxo oxygens. Twelve phosphonate groups and six -OH groups act as bridging ligands and bind six Fe octahedra. Because of protonation of the amino group, the phosphonate anions coordinate in the zwitterionic form as HAIPA(-) (NH3+(CH3)(2)CPO32-). The iron cations are present in the form of high-spin Fe3+, which was confirmed by the bond valence sum (BVS) calculations and the Fe-57 Mossbauer spectra. The magnetic measurements show antiferromagnetic coupling between the iron centers with decreasing temperature.

机译：一种新的六核分子铁膦酸酯配合物，[Fe基6（海帕）（12）（OH）（6）]中心点NH（2）O（1个中心的点N（2）O）（H（2）AIPA = NH2 （CH 3）（2）CP（O）（OH）（2），（2-氨基丙-2-基）膦酸），由Fe2 +和Fe3 +的盐通过与配体相互作用的盐合成水。对应的H2AIPA的钠或四甲基铵的盐的量，以铁前体导致的复杂1.分离的产物大亮绿色晶体形成的溶液中加入通过光谱和分析方法研究-IR，穆斯堡尔谱，TG / DSC， ICP-OES和CHN分析。 1一种新型{的Fe-6}六核分子结构通过单晶X射线衍射分析证实。铁阳离子的八面体配位环境是由膦酸盐和羟氧形成。十二膦酸酯基团和六个-OH基团作为桥连配体和绑定6个八面体的Fe。因为氨基的质子化，膦酸酯阴离子坐标在两性离子形式如海帕（ - ）（NH 3 +（CH 3）（2）CPO32-）。的铁阳离子存在于高自旋的Fe3 +，这是由键价总和（BVS）的计算和Fe 57穆斯堡尔谱证实的形式。磁性测量显示随着温度的降低铁中心之间的反铁磁耦合。

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来源
《New Journal of Chemistry》 |2018年第3期|共8页
作者
Doroshenko Iaroslav; Babiak Michal; Buchholz Axel; Tucek Jiri; Plass Winfried; Pinkas Jiri;
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Masaryk Univ Dept Chem Kotlarska 2 CZ-61137 Brno Czech Republic;

Masaryk Univ Dept Chem Kotlarska 2 CZ-61137 Brno Czech Republic;

Friedrich Schiller Univ Jena Inst Anorgan &

Analyt Chem Humboldtstr 8 D-07743 Jena Germany;

Palacky Univ Reg Ctr Adv Technol &

Mat Fac Sci Slechtitelu 27 CZ-78371 Olomouc Czech Republic;

Friedrich Schiller Univ Jena Inst Anorgan &

Analyt Chem Humboldtstr 8 D-07743 Jena Germany;

Masaryk Univ Dept Chem Kotlarska 2 CZ-61137 Brno Czech Republic;

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Hexanuclear iron(III) alpha-aminophosphonate: synthesis, structure, and magnetic properties of a molecular wheel

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