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Inorg Chem. 2010 Jul 5;49(13):5971-6. doi: 10.1021/ic100518b.

Efficient synthetic strategy to construct three-dimensional 4f-5d networks using neutral two-dimensional layers as building blocks.

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  • 1School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China.


The reaction of neutral two-dimensional (2D) layer Tb(H(2)O)(5)W(CN)(8) with pyrazine in the acetonitrile solution has led to a 3D bimetallic complex, Tb(H(2)O)(4)(pyrazine)(0.5)W(CN)(8) (1). In the structure of 1, the eight-coordinated W center adopts a slightly distorted dodecahedron, while the Tb center exhibits a nine-coordinated slightly distorted tricapped trigonal prism. The Tb(3+) atoms and the [W(CN)(8)](3-) units are linked in alternating fashion in the ab crystallographic plane, resulting in an infinite 2D corrugated layers. The linear bis-monodentate pyrazine ligands acting as pillars link adjacent layers along the c axis to form an extended 3D open framework. The possible formation mechanism is proposed, and the temperature has played a crucial role for the formation of 1. Magnetic measurements revealed the presence of ferromagnetic interaction between Tb(III) and W(V) centers. 1 marks the first structural pattern using the neutral 2D layer as building block and the first 3D complex with Ln(III)-[W(V)(CN)](8) found in octacyanometallate-based system. Such a novel and effective building-block methodology will provide a new attractive path forward in developing functionalities of 3D 4f-5d system and may provide an opportunity to obtain 3D magnet in 4f-5d assembly.

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