Synthesis and characterization of fluoride-incorporated polyoxovanadates.
Synthesis and characterization of fluoride-incorporated polyoxovanadates.
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DOI：
10.1016/j.jinorgbio.2015.02.010
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发表时间：
2015-06
影响因子：
3.9
通讯作者：
Yuji Kikukawa;T. Yokoyama;Sanae Kashio;Y. Hayashi
中科院分区：
文献类型：
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作者：
Yuji Kikukawa;T. Yokoyama;Sanae Kashio;Y. Hayashi
钒氧酸盐的形态研究对于阐明其生物活性至关重要。我们调查了钒氧酸盐物种的分布在卤阴离子的存在下，在不同的酸浓度在水溶液中的混合溶剂系统。氯离子、溴离子和碘离子的存在对在51 V NMR中观察到的多钒酸盐物种的出现没有影响。这些都是偏钒酸盐和十钒酸盐形成的先例。氟离子的存在下，在加入酸表现出强烈的干预，在多钒酸盐的平衡，我们发现随后形成的两个多钒酸盐物种通过51 V NMR观察。从估计的实验条件下，我们成功地分离了氟掺入的多氧钒酸盐{Et 4 N}4[V7 O 19 F]和{Et 4 N}4[HV 11 O29 F2]。聚阴离子[V7 O 19 F]4 −是一种全V（V）态的多钒酸盐，在一个阴离子结构完整性内具有四面体和四方锥钒单元的两种不同配位环境。基于四面体单元的偏钒酸盐和基于八面体单元的十钒酸盐结构之间的结构间隙可以通过这种混合络合物连接。
The speciation studies of oxovanadates are essential to clarify their biological activities. We surveyed the distribution of oxovanadate species in the presence of halide anions with various acid concentrations in an aqueous mixed-solvent system. The presence of chloride, bromide, and iodide anions has no effects on the appearance of polyoxovanadate species observed in51V NMR. Those are the precedent formation of metavanadate species and decavanadates. The presence of fluoride anion during the addition of acids exhibits strong intervention in the polyoxovanadate equilibria and we found the subsequent formation of two polyoxovanadate species by51V NMR observation. From the estimated experimental condition, we isolated fluoride-incorporated polyoxovanadates {Et4N}4[V7O19F] and {Et4N}4[HV11O29F2], successfully. Polyanion [V7O19F]4 −is the fluoride-incorporated all V(V) state polyoxovanadate which has two different coordination environments of tetrahedral and square pyramidal vanadium units within the one anionic structural integrity. The structural gap between tetrahedral-unit-based metavanadate and octahedral-unit-based decavanadate structures may be linked by this hybrid complex.