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使用桥联二苯基膦酸酯制备金属-有机杂化结构:合成、表征、磁性及弱相互作用对其晶体堆积的影响。

Fabrication of metal-organic hybrid architectures using bridging diphenyl phosphate: syntheses, characterization, magnetic properties and the effect of weak interactions on their crystal packing.

机构信息

Department of Chemistry, Jadavpur University, Jadavpur, Kolkata 700 032, India.

出版信息

Dalton Trans. 2013 Feb 14;42(6):2094-106. doi: 10.1039/c2dt32057f.

DOI:10.1039/c2dt32057f
PMID:23187633
Abstract

Ten different metal-organic hybrids of divalent metal ions have been synthesized using the diphenyl phosphate ligand and three different N,N donor spacers. All the complexes have been characterized by single crystal X-ray crystallography and other physico-chemical methods. For six complexes, the diphenyl phosphate (dpp) ligand acts as a bridge between the metal ions, whereas in four complexes dpp acts as a monodentate ligand. All nine complexes (1-9) show two dimensional coordination structures created by the N,N donor spacers, and, the remaining one (10) has a one dimensional ribbon-like structure. Here the aromatic rings present in the compounds viz. phenyl rings of dpp and the pyridyl rings of N,N donor spacers, have a key role to extend the dimensionality in their solid-state structures. In each instance, the aromatic rings of dpp and N,N donor spacers are nicely involved in the supramolecular structure generation by the help of π-π interactions. In all the cases, the role of weak interactions on the crystal packing and their effect in the generation of different supramolecular architectures has been thoroughly investigated. Variable temperature magnetic measurements of three relevant complexes have been carried out. Compounds 1 and 3 clearly indicate the existence of a weak antiferromagnetic interaction between the metal ions through the bridging dpp ligand. In 5, where dpp acts as a monodentate ligand; the metal ion may be considered as an isolated monomer.

摘要

已经使用二苯基膦配体和三种不同的 N,N 供体间隔物合成了十种不同的二价金属离子的金属有机杂化物。所有配合物均通过单晶 X 射线晶体学和其他物理化学方法进行了表征。对于六个配合物,二苯基膦(dpp)配体充当金属离子之间的桥联配体,而在四个配合物中,dpp 充当单齿配体。所有九个配合物(1-9)均显示出由 N,N 供体间隔物形成的二维配位结构,而另一个配合物(10)具有一维带状结构。此处,化合物中存在的芳环,即 dpp 的苯基环和 N,N 供体间隔物的吡啶环,在其固态结构中具有扩展维度的关键作用。在每种情况下,dpp 和 N,N 供体间隔物的芳环都通过π-π相互作用很好地参与了超分子结构的生成。在所有情况下,都彻底研究了弱相互作用对晶体堆积的作用及其在生成不同超分子结构中的作用。对三个相关配合物的变温磁测量已经进行。配合物 1 和 3清楚地表明,通过桥联 dpp 配体,金属离子之间存在弱反铁磁相互作用。在 5 中,dpp 充当单齿配体;金属离子可以被认为是孤立的单体。

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