Wendt Michael, Warzok Ulrike, Näther Christian, van Leusen Jan, Kögerler Paul, Schalley Christoph A, Bensch Wolfgang
Institut für Anorganische Chemie , Christian-Albrechts-Universität zu Kiel , Max-Eyth-Str. 2 , 24118 Kiel , Germany . Email:
Institut für Chemie und Biochemie der Freien Universität , Takustr. 3 , 14195 Berlin , Germany . Email:
Chem Sci. 2016 Apr 21;7(4):2684-2694. doi: 10.1039/c5sc04571a. Epub 2016 Jan 8.
Antimonato polyoxovanadate (POV) cluster compounds {M(en)}[VSbO(HO) ]·HO (M = Fe, Co, Ni and = 0 or 1) obtained under solvothermal conditions exhibit unusual high water solubility making these compounds promising synthons for generation of new POV structure types. Electrospray ionization mass spectrometry provides evidence (i) for a water molecule encapsulated inside the cavity of a fraction of the spherical cluster shells, (ii) for a post-functionalization in water, namely a slow exchange of VO against SbO, (iii) for the inner-phase reactivity of the encapsulated water that is capable of opening an oxo-bridge, and (iv) for a significant acceleration of the O/O exchange reactions of oxygen atoms in the cluster periphery with surrounding HO, when encapsulated water is present. To the best of our knowledge, this is the first example in polyoxovanadate chemistry for the transduction of inner-phase reactivity of an encapsulated guest molecule into changes in the outer-phase reactivity of the cluster. Magnetic susceptibility measurements reflect the individual contributions of the frustrated {V} spin polytope and the {M(en)} complexes, with very weak coupling between these groups.
在溶剂热条件下获得的锑多氧钒酸盐（POV）簇合物{M(en)}[VSbO(HO) ]·HO（M = Fe、Co、Ni， = 0或1）表现出异常高的水溶性，这使得这些化合物成为生成新型POV结构类型的有前景的合成子。电喷雾电离质谱提供了以下证据：（i）在一部分球形簇壳的腔内封装有一个水分子；（ii）在水中进行后功能化，即VO与SbO的缓慢交换；（iii）封装水的内相反应性能够打开一个氧桥；（iv）当存在封装水时，簇外围的氧原子与周围HO的O/O交换反应显著加速。据我们所知，这是多氧钒酸盐化学中首次将封装客体分子的内相反应性转化为簇外相反应性变化的例子。磁化率测量反映了受挫的{V}自旋多面体和{M(en)}配合物的各自贡献，这些基团之间的耦合非常弱。
