Diphosphoryl-functionalized Polyoxometalates: Structurally and Electronically Tunable Hybrid Molecular Materials
Diphosphoryl-functionalized Polyoxometalates: Structurally and Electronically Tunable Hybrid Molecular Materials
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二磷酰基功能化多金属氧酸盐：结构和电子可调的杂化分子材料
DOI：
10.1002/ange.202302446
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发表时间：
2023
影响因子：
--
通讯作者：
Amin S
中科院分区：
文献类型：
--
作者：
Amin S
本文中，我们报道了一类新的杂合Wells-Dawson聚氧乙烯酸酯（POM）的合成和表征，其含有通式[P2 W17 O 57（P2 O 6X）]6-（X=O，NH，或CR 1 R2）的二磷酰基（P2 O 6X）。发现修饰桥连单元X会影响POM的氧化还原电位。可以容易地制备一系列α-官能化的二膦酸（X= CR 1 R2），这提供了获得多种官能化的杂化POM的可能性。与现有的膦酸酯杂化Wells-Dawson POM相比，二磷酰基取代的POM提供了更宽的可调氧化还原窗口和增强的水解稳定性。该研究为下一代杂化Wells-Dawson多金属氧酸盐的合理设计和合成提供了基础。
Herein, we report the synthesis and characterization of a new class of hybrid Wells–Dawson polyoxometalate (POM) containing a diphosphoryl group (P2O6X) of the general formula [P2W17O57(P2O6X)]6−(X=O, NH, or CR1R2). Modifying the bridging unit X was found to impact the redox potentials of the POM. The ease with which a range of α‐functionalized diphosphonic acids (X=CR1R2) can be prepared provides possibilities to access diverse functionalized hybrid POMs. Compared to existing phosphonate hybrid Wells–Dawson POMs, diphosphoryl‐substituted POMs offer a wider tunable redox window and enhanced hydrolytic stability. This study provides a basis for the rational design and synthesis of next‐generation hybrid Wells–Dawson POMs.