Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

Abstract

The Preyssler polyoxoanion, [NaP5W30O110]14− ({P5W30}), 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 Co2+‐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+, Mg2+, or Ca2+ in the framework synthesis is used to selectively synthesize five different Co2+‐bridged {P5W30} structures. The influence of the competition between K+ and Co2+ for binding to {P5W30} 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.

POMzites: A roadmap for inverse design in metal oxide chemistry

“…In a further recent study, Schimpf and her team discovered that the competition between K + and Co 2+ for binding to {P 5 W 30 } dictates the formation of the framework. [ 31 ] Their findings provide a deep insight into the factors that govern the formation of metal‐bridged POM‐based porous networks.…”

Polyoxometalates‐Based Semi‐flexible Metal‐Semiconductor Triboelectric Nanogenerators for Low Frequency and Small Amplitude Mechanical Energy Harvesting

“…Polyoxometalates (POMs), an effective electronic transmission medium, have the advantages of simple synthesis, lowcost, redox reversibility and excellent stability. [31][32][33][34][35][36][37][38] In the past ten years, our research team has introduced POMs into dyesensitized solar cells (DSSCs) and proved that POMs are a class of good electronic transmission medium that can store and export electrons quickly. [39][40][41][42][43][44][45][46][47] In addition, we also applied POMs to the electrode materials of the piezoelectric nanogenerator (PENG), a flexible transparent device which can convert mechanical energy into electricity effectively and further confirmed that POMs as good electron transport medium can be used in energy conversion devices.…”

“…Polyoxometalates (POMs), an effective electronic transmission medium, have the advantages of simple synthesis, low‐cost, redox reversibility and excellent stability [31–38] . In the past ten years, our research team has introduced POMs into dye‐sensitized solar cells (DSSCs) and proved that POMs are a class of good electronic transmission medium that can store and export electrons quickly [39–47] .…”

Directional Bonding in Decaniobate Inorganic Frameworks

“…However, with the addition of heterometals (other transition metals, p‐block metals, lanthanides and actinides), many inorganic frameworks have been isolated (i.e. [5–10]). With the addition of a heterometal and an organic ditopic linker, POM‐based MOFs can be isolated [5, 11–14] …”

“…Polyoxometalates (POMs) are anionic metal-oxo clusters, characteristic of early d 0 transition metals including V V ,N b V , Ta V ,M o VI and W VI .T hey are terminated by multiply bonded oxo groups,w hich generally prevents the formation of frameworks.H owever,w ith the addition of heterometals (other transition metals,p -block metals,l anthanides and actinides), many inorganic frameworks have been isolated (i.e. [5][6][7][8][9][10]). With the addition of ah eterometal and an organic ditopic linker,P OM-based MOFs can be isolated.…”