Insertion of VIV Ions into the Polyoxotungstate Archetype {As4W40}.
Insertion of VIV Ions into the Polyoxotungstate Archetype {As4W40}.
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DOI：
10.1021/acs.inorgchem.1c00897
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发表时间：
2021-05
影响因子：
4.6
通讯作者：
M. Stuckart;N. Izarova;Maria Glöß;Jennifer Klose;C. Schmitz-Antoniak;P. Kögerler;B. Kersting;K. Monakhov
中科院分区：
文献类型：
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作者：
M. Stuckart;N. Izarova;Maria Glöß;Jennifer Klose;C. Schmitz-Antoniak;P. Kögerler;B. Kersting;K. Monakhov
合成了一种新的多氧六环酸盐化合物，其结构为（NH 4）22[（VIVO）2（VIVO（H2O））（AsIIIWVI 9 O33）2（AsIIIWVI8.5VIV0.5（OH）O32）2（WVIO 2）4]·48 H2O（NH 4-As 4 W39（V4））。SQUID磁强计显示三个弱耦合VIV中心与反铁磁交换相互作用和一个孤立的VIV离子作为自旋1/2居里顺磁体。紫外-可见光谱表明As 4 W39（V4）结构在水溶液中至少24 h保持完整。为了使As 4 W39（V4）能够从溶液沉积在金表面上，制备其三己基十四烷基鏻盐THTDP-As 4 W39（V4）。这两种同系物的红外光谱揭示了As 4 W39（V4）的结构特征，与抗衡阳离子无关。X射线吸收近边结构数据证实了NH_4-As_4W_39（V_4）和THTDP-As_4 W_39（V_4）中存在畸变四方锥配位几何结构的VIV中心。沉积在Au（111）上的后者的X射线光电子能谱表明，4 V和35 W中心保持其IV+和VI+氧化态，而剩余的4 W离子被还原为IV+。
A new polyoxometalate compound consisting of the 39-tungsto-4-arsenate(III) unit with four incorporated VIV ions, isolated as (NH4)22[(VIVO)2(VIVO(H2O))(AsIIIWVI9O33)2(AsIIIWVI8.5VIV0.5(OH)O32)2(WVIO2)4]·48H2O (NH4-As4W39(V4)), was synthesized and fully characterized. SQUID magnetometry shows three weakly coupled VIV centers with an antiferromagnetic exchange interaction and one isolated VIV ion as a spin-1/2 Curie paramagnet. UV-vis spectroscopy indicates that the As4W39(V4) structure remains intact in aqueous solution for at least 24 h. To enable the deposition of As4W39(V4) from solution on gold surfaces, its trihexyltetradecylphosphonium salt, THTDP-As4W39(V4), was prepared. The IR spectra of both congeners reveal the structural identity of As4W39(V4) independent of the countercations. The X-ray absorption near-edge structure data confirm the presence of VIV centers in a distorted square-pyramidal coordination geometry in NH4-As4W39(V4) and THTDP-As4W39(V4). X-ray photoelectron spectroscopy of the latter, deposited on Au(111), shows that the 4 V and 35 W centers preserve their IV+ and VI+ oxidation states, while the remaining 4 W ions are reduced to IV+.