Chen Linfeng, Turo Michael J, Gembicky Milan, Reinicke Ruth A, Schimpf Alina M
Department of Chemistry and Biochemistry, University of California, San Diego, USA.
Angew Chem Int Ed Engl. 2020 Sep 14;59(38):16609-16615. doi: 10.1002/anie.202005627. Epub 2020 Jul 21.
The Preyssler polyoxoanion, [NaP W O ] ({P W }), is used as a platform for evaluating the role of nonbridging cations in the formation of transition-metal-bridged polyoxometalate (POM) coordination frameworks. Specifically, the assembly architecture of Co -bridged frameworks is shown to be dependent on the identity and amount of alkali or alkaline-earth cations present during crystallization. The inclusion of Li , Na , K , Mg , or Ca in the framework synthesis is used to selectively synthesize five different Co -bridged {P W } structures. The influence of the competition between K and Co for binding to {P W } in dictating framework assembly is evaluated. The role of ion pairing on framework assembly structure and available void volume is discussed. Overall, these results provide insight into factors governing the ability to achieve controlled assembly of POM-based coordination networks.
普雷斯勒多金属氧酸盐阴离子[NaP5W30O110]14−（{P5W30}）被用作一个平台，用于评估非桥连阳离子在过渡金属桥连多金属氧酸盐（POM）配位框架形成中的作用。具体而言，钴桥连框架的组装结构被证明取决于结晶过程中存在的碱金属或碱土金属阳离子的种类和数量。在框架合成中加入Li+、Na+、K+、Mg2+或Ca2+用于选择性地合成五种不同的钴桥连{P5W30}结构。评估了K+和Co2+在与{P5W30}结合时的竞争对框架组装的影响。讨论了离子配对对框架组装结构和可用空隙体积的作用。总体而言，这些结果为控制基于POM的配位网络实现可控组装的能力的相关因素提供了见解。
