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Syntheses, Structures and Magnetic Properties of New Octacyanometallate-based Coordination Polymers

Author: QianSuYan
Tutor: YuanAiHua
School: Jiangsu University of Science and Technology
Course: Applied Chemistry
Keywords: octacyanometallates nickel rare-earth crystal structures magnetic properties
CLC: O641.4
Type: Master's thesis
Year: 2011
Downloads: 13
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Abstract


This paper reviews the development in the field of octacyanometallate-based complexes, and fourteen new octacyanometallate-based hetero-bimetallc complexes have been synthesized using [M（CN）8]3-/4- （M = Mo, W） as building blocks.Octacyanometallate-based complexes involving [Ni（L）]2+ precursors: four new complexes [H2（L1）]0.5[NiII（L1）][WV（CN）8]·2DMF·H2O （1）, [NiII（L2）]3[WV（CN）8]2·4H2O （2）, [NiII（L3）]2[MoIV（CN）8]·3DMF·2H2O （3） and [NiII（L4）]2[WIV（CN）8]·4DMF·4H2O （4） have been obtained, using [M（CN）8]3-/4- and [Ni（macrocyclic ligands）]2+ as building blocks. In the structure of 1, [W（CN）8]3- and [Ni（L1）]2+ moieties are linked in an alternating fashion to form a 1D chain structure, which is further inter-linked through interchain hydrogen bonding, resulting in the formation of a supermolecular network. Magnetic studies indicate 1 is a metamagnet. Complex 2 is 2D graphite-like layers with （6,3） topology and also exhibits metamagnetic behaviour. In the structure of 3 and 4, [M（CN）8]4- and [Ni（L）]2+ units are linked alternatively to form a 3D diamond-type topological structure. Both complexes show a weak antiferromagnetic interaction between Ni（II） ions.Octacyanometallate-based complexes involving rare-earth metal ions: four types of complexes have been obtained, using [M（CN）8]3- and rare-earth metal ions as building blocks with various chelated ligands. Firstly, for three complexes [Ln（H2O）4（CH3CN）2] [M（CN）8]·2CH3CN （Ln = La, M = Mo, 5, W, 6; Ln = Ce, M = W, 7） with 1D ladder-like chain structure, each {LnIIIMV} chain interacts through hydrogen-bonding with six other surrounding chains to form a 3D supramolecular network. Secondly, four complexes [Sm（phen）2（H2O）2Mo（CN）8]2[（n-C4H9）4N]（NO3）·2CH3CN·8H2O （8）, [Sm（tmphen）2 （DMF）2][W（CN）8]·2H2O （9） and [Pr（tmphen）（DMF）5][M（CN）8]·DMF·2H2O （M = Mo, 10; W, 11） exhibit a 1D helical chain structure, which is futher linked throughπ-πstacking and van der Waals interaction, leading to the formation of a 3D supermolecular network. Complexes 10-11 show an antiferromagnetic interaction between Pr（III） centers. Thirdly, two complexes [Sm（phen）（DMF）5][M（CN）8]·2H2O （M = Mo, 12; W, 13） have a 1D zigzag chain structure, which is futher linked throughπ-πstacking and van der Waals interaction, resulting in the formation of a 3D supermolecular network. Interestingly, magnetic studies show that 12-13 exhibited ferromagnetic in 2 kOe and antiferromagnetic behavior in 100 Oe. The last type is an ionic complex [Tb（4,4’-bpdo）4（H2O）4][Mo（CN）8] （14）, in which [Mo（CN）8] and [Tb（4,4’-bpdo）4（H2O）4] interact throughπ-πstacking and van der Waals interaction, leading to the formation of a supermolecular network.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )
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