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Nickel(II) 3,4;9,10-Perylenediimide bis-Phosphonate Pentahydrate: AudMetal−Organic Ferromagnetic Dye

机译:3,4; 9,10-Per二酰亚胺双膦酸镍五水合物:A ud金属有机铁磁染料

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摘要

The new metal−organic compound nickel(II) 3,4;9,10-udperylenediimide bis-phosphonate pentahydrate, i.e. Ni2[(PDI-BP)-ud(H2O)2]·3H2O (1), has been synthesized and its structural and magneticudproperties have been studied. Reaction of 3,4;9,10-perylenediimide bisphosphonateud(PDI-BP, hereafter) ligand and nickel chloride in water resultedudin the precipitation of a red and poorly crystalline solid (1). As the solid showsuda poor crystalline organization of aggregates, the energy dispersive X-rayuddiffraction analysis (EDXD) technique has been used to obtain short-rangeudorder structural information of the single nanoaggregates by radial distributionudfunction analysis. The overall structure of the compound is characterized byudlayers containing perylene planes shifted in the direction perpendicular to theudstacking axes in such a way that only the outer rings overlap. The edges of theudperylene planes are connected to the phosphonate groups through an imidoudgroup. The oxygen atoms of the [−PO3]2‑ group and those of the waterudmolecules are bonded to the nickel ions resulting in a [NiO6] octahedral coordination sphere. The Ni−O bond lengths are 0.21ud± 0.08 nm and the Ni−O−Ni angles of aligned moieties are 95 ± 2°. The oxygen atoms of the water molecules and the nickeludatoms are nearly planar and almost perpendicular to the perylene planes forming chains of edge-sharing octahedra. The magneticudproperties of (1) show the presence of intrachain ferromagnetic Ni−Ni interactions and a long-range ferromagnetic order belowud21 K with a canting angle and with a spin glasslike behavior due to disorder in the inorganic layer. Hysteresis cycles show audcoercive field of ca. 272 mT at 2 K that decreases as the temperature is increased and vanishes at ca. 20 K.
机译:合成了新的金属有机化合物镍(II)3,4; 9,10-二ud二酰亚胺双膦酸酯五水合物,即Ni2 [(PDI-BP)-ud(H2O)2]·3H2O(1)对其结构和磁性能进行了研究。 3,4; 9,10-per二酰亚胺双膦酸酯 ud(PDI-BP,此后)配体与氯化镍在水中的反应导致红色和结晶性较弱的固体沉淀(1)。由于固体显示聚集体的晶体组织较差,因此已使用能量色散X射线扩散分析(EDXD)技术通过径向分布功能泛函分析获得了单个纳米聚集体的短距离无序结构信息。该化合物的整体结构的特征在于包含二萘嵌苯平面的覆盖层在垂直于堆叠轴的方向上偏移,使得仅外环重叠。 ud平面的边缘通过亚氨基ud基团连接至膦酸酯基团。 [-PO3] 2-的氧原子和水分子的氧原子与镍离子结合,形成[NiO6]八面体配位球。 Ni-O键长为0.21 ud±0.08 nm,排列部分的Ni-O-Ni角为95±2°。水分子和镍原子硅原子的氧原子几乎是平面的,并且几乎垂直于per平面,从而形成了边缘共享八面体的链。 (1)的磁特性表明存在链内铁磁Ni-Ni相互作用和ud21 K以下的长距离铁磁序,具有倾斜角,并且由于无机层的无序具有自旋玻璃状的行为。磁滞回线显示的屈服场。在2 K时为272 mT,随着温度的升高而降低,并在大约20 K时消失。 20K。

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