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一种新型夹心型多钨磷酸化合物，其中包含两种类型的金属位于中环：M'2M2(PW9O34)(2)(12-)（M'=Na 或 Li，M=Mn2+，Co2+，Ni2+和 Zn2+）。

A new family of sandwich-type polytungstophosphates containing two types of metals in the central belt: M'2M2(PW9O34)(2)(12-) (M' = Na or Li, M = Mn2+, Co2+, Ni2+, and Zn2+).

机构信息

Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.

出版信息

Inorg Chem. 2010 May 3;49(9):4125-32. doi: 10.1021/ic9024712.

DOI:10.1021/ic9024712
PMID:20359244
Abstract

A new family of sandwich-type polytungstophosphates containing two different types of metals in the central belt, M'(2)M(2)(PW(9)O(34))(2)(12-) (M' = Na or Li, M = Mn(2+), Co(2+), Ni(2+), and Zn(2+)), have been synthesized and characterized by infrared spectroscopy, (31)P solution NMR spectroscopy, and elemental analysis. Compounds Na(2)Co(2)(PW(9)O(34))(2)(12-) (Na2Co2), Na(2)Ni(2)(PW(9)O(34))(2)(12-) (Na2Ni2), Li(2)Ni(2)(PW(9)O(34))(2)(12-) (Li2Ni2), Na(2)Mn(2)(PW(9)O(34))(2)(12-) (Na2Mn2), and Li(2)Zn(2)(PW(9)O(34))(2)(12-) (Li2Zn2) were characterized by X-ray crystallography. All these compounds have similar structures, in which two transition-metal ions and two alkali metal ions (sodium or lithium) are sandwiched between two B-alpha-PW(9)O(34) units; the transition and alkali metals reside in the internal and external (solvent exposed) positions of the central belt, respectively. By adding LiCl to aqueous solutions of compounds Na2M2, lithium-sodium exchanges in the external belt positions are observed by (31)P solution NMR spectroscopy and X-ray crystallography. Magnetic measurements indicate ferromagnetic exchange interactions between the two Ni(2+) ions in Na2Ni2 at 10-300 K and the two Co(2+) ions in Na2Co2 at 6-30 K. In contrast, Na2Mn2 exhibits an antiferromagnetic interaction between the Mn(2+) ions at 2-50 K.

摘要

一种新型夹心型多钨磷酸化合物，其中包含两种不同类型的金属位于中央带，M'(2)M(2)(PW(9)O(34))(2)(12-) (M' = Na 或 Li，M = Mn(2+)，Co(2+)，Ni(2+)和 Zn(2+)），已经通过红外光谱，(31)P 溶液 NMR 光谱和元素分析进行了合成和表征。化合物 Na(2)Co(2)(PW(9)O(34))(2)(12-) (Na2Co2)，Na(2)Ni(2)(PW(9)O(34))(2)(12-) (Na2Ni2)，Li(2)Ni(2)(PW(9)O(34))(2)(12-) (Li2Ni2)，Na(2)Mn(2)(PW(9)O(34))(2)(12-) (Na2Mn2)和 Li(2)Zn(2)(PW(9)O(34))(2)(12-) (Li2Zn2) 通过 X 射线晶体学进行了表征。所有这些化合物都具有相似的结构，其中两个过渡金属离子和两个碱金属离子（钠或锂）夹在两个B-alpha-PW(9)O(34)单元之间；过渡金属和碱金属分别位于中央带的内部和外部（暴露于溶剂的位置）。通过向化合物 Na2M2 的水溶液中添加 LiCl，通过(31)P 溶液 NMR 光谱和 X 射线晶体学观察到外部带位置的锂-钠交换。磁性测量表明，在 10-300 K 温度范围内，Na2Ni2 中两个 Ni(2+)离子之间存在铁磁交换相互作用，在 6-30 K 温度范围内，Na2Co2 中两个 Co(2+)离子之间存在铁磁交换相互作用。相比之下，在 2-50 K 温度范围内，Na2Mn2 中 Mn(2+)离子之间存在反铁磁相互作用。

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