Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany.
Chem Soc Rev. 2015 Dec 7;44(23):8443-83. doi: 10.1039/c5cs00531k. Epub 2015 Sep 7.
Polyoxovanadates (POVs), known for their wide applicability and relevance in chemical, physical and biological sciences, are a subclass of polyoxometalates and usually self-assemble in aqueous-phase, pH-controlled condensation reactions. Archetypical POVs such as the robust VO42 polyoxoanion can be structurally, electronically and magnetically altered by heavier group 14 and 15 elements to afford Si-, Ge-, As- or Sb-decorated POV structures (heteroPOVs). These main-group semimetals introduce specific chemically engineered functionalities which cause the generally hydrophilic heteroPOV compounds to exhibit interesting reactivity towards organic molecules, late transition metal and lanthanoid ions. The fully-oxidised (V(V)), mixed-valent (V(V)/V(IV) and V(IV)/V(III)), "fully-reduced" (V(IV)) and "highly-reduced" (V(III)) heteroPOVs possess a number of intriguing properties, ranging from catalytic to molecular magnet characteristics. Herein, we review key developments in the synthetic and structural chemistry as well as the reactivity of POVs functionalised with Si-, Ge-, As- or Sb-based heterogroups.
多金属氧酸盐（POVs）因其在化学、物理和生物科学中的广泛适用性和相关性而闻名，是多金属氧酸盐的一个子类，通常在水相、pH 控制的缩合反应中自组装。典型的 POV 如坚固的VO42多氧阴离子可以通过较重的第 14 族和第 15 族元素在结构、电子和磁性上进行修饰，以提供 Si、Ge、As 或 Sb 修饰的 POV 结构（杂 POV）。这些主族半金属引入了特定的化学工程功能，使通常亲水的杂 POV 化合物对有机分子、后过渡金属和镧系元素离子表现出有趣的反应性。完全氧化（V(V)）、混合价态（V(V)/V(IV)和 V(IV)/V(III)）、“完全还原”（V(IV)）和“高度还原”（V(III)）杂 POV 具有许多有趣的性质，从催化到分子磁特性。在此，我们综述了 Si、Ge、As 或 Sb 基杂基团功能化的 POVs 的合成和结构化学以及反应性方面的关键进展。
