Production and reactions of organic-soluble lanthanide complexes of the monolacunary Dawson [α1-P2W17O61]10- polyoxotungstate
Production and reactions of organic-soluble lanthanide complexes of the monolacunary Dawson [α1-P2W17O61]10- polyoxotungstate
复制标题
DOI：
10.1021/ic051679g
复制
发表时间：
2006-02-06
影响因子：
4.6
通讯作者：
Tabet, JC
中科院分区：
文献类型：
--
作者：
Boglio, C;Lenoble, G;Tabet, JC
在多金属氧酸盐中掺入稀土元素提供了一种新的潜在有用的材料类别，它们结合了这两种成分的固有性质。为了利用[α(1)-Ln(H2O)(4)P2W17O61](7-)物种在催化和发光材料开发中的应用，发展了这一族稀土多金属氧酸盐在有机溶剂中的化学。合成了有机可溶的多金属氧酸盐-稀土配合物TBA(5)H(2)[α(1)-Ln(H2O)(4)P2W17O61](Ln=La(III)，Sm(III)，Eu(III)，Yb(III))，通过元素分析、酸碱滴定、红外光谱、P-31核磁共振和质谱分析对其结构进行了表征。合成过程包括在严格的pH控制下在水溶液中进行阳离子歧化反应。固-液相转移法合成了一个独特的物种(TBA)(8)K-3[Yb(α(1)-YbP2W17O61)(2)]，其中含有三个Yb离子和两个[α(1)-P2W17O61](10-)多氧钨酸根。从水溶液中结晶出中心对称二聚体配合物[{α(1)-La(H2O)(4)P2W17O61}(2)](14-)，并用X-射线衍射法对其进行了表征。对配合物TBA(5)H(2)[α(1)-Ln(H2O)(4)P2W17O61]的ESI质谱分析表明，在有机溶液中也存在类似的二聚体，特别是对于早期的稀土元素。从干乙腈溶液中分离出的络合物在质谱计中的碎裂包括一个氧代配体的双质子化和一个水分子的损失。低质量的钨酸盐碎片结合成[(WO_3)(N)](2-)(n=1-5)离子及其与磷酸盐的缩合产物。TBA(5)H(2)[α(1)-Eu(H2O)(4)P2W17O61]与1，10-二氮杂菲或2，2‘-联吡啶的反应使Eu的发光增强。这一结果是由[α(1)-Eu-(H2O)(4)P2W17O61](7-)三元络合物和两个敏化配体形成的。
The incorporation of lanthanides into polyoxometalates provides entry to new classes of potentially useful materials that combine the intrinsic properties of both constituents. To utilize the [alpha(1)-Ln(H2O)(4)P2W17O61](7-) species in applications of catalysis and development of luminescent materials, the chemistry of this family of lanthanide polyoxometalates in organic solvents has been developed. Organic-soluble polyoxometalate-lanthanide complexes TBA(5)H(2)[alpha(1)-Ln(H2O)(4)P2W17O61] (Ln = La(III), Sm(III), Eu(III), Yb(III)) were prepared and characterized by elemental analysis, acid-base titration, IR, P-31 NMR, and mass spectrometry. The synthetic procedure involves a cation metathesis reaction in aqueous solution under strict pH control. A solid-liquid-phase transfer protocol yielded a unique species (TBA)(8)K-3[Yb(alpha(1)-YbP2W17O61)(2)] with three ytterbium ions and two [alpha(1)-P2W17O61](10-) polyoxotungstates. A centrosymmetric dimeric complex [{alpha(1)-La(H2O)(4)P2W17O61}(2)](14-) was crystallized from aqueous solution and characterized by X-ray diffraction. ESI mass spectral analysis of the complexes TBA(5)H(2)[alpha(1)-Ln(H2O)(4)P2W17O61] shows that similar dimers exist in organic solution, in particular for the early lanthanides. Fragmentation in the mass spectrometer of the complexes from dry acetonitrile solution involves double protonation of an oxo ligand and loss of one water molecule. Low mass tungstate fragments combine into [(WO3)(n)](2-) (n = 1-5) ions and their condensation products with phosphate. Reaction of TBA(5)H(2)[alpha(1)-Eu(H2O)(4)P2W17O61] with 1,10-phenanthroline or 2,2'-bipyridine showed an increase of the europium luminescence. This result is explained by the formation of a ternary complex of [alpha(1)-Eu-(H2O)(4)P2W17O61](7-) and two sensitizing ligands.