Space-Confined Nucleation of Semimetal-Oxo Clusters within a [H7P8W48O184]33- Macrocycle: Synthesis, Structure, and Enhanced Proton Conductivity.
Space-Confined Nucleation of Semimetal-Oxo Clusters within a [H7P8W48O184]33- Macrocycle: Synthesis, Structure, and Enhanced Proton Conductivity.
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DOI：
10.1021/acs.inorgchem.2c03543
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发表时间：
2022-12
影响因子：
4.6
通讯作者：
Yilin Niu;Yue Ding;Hongxin Sheng;Sai Sun;Chaoqin Chen;Jing Du;Hong‐Ying Zang;Peng Yang
中科院分区：
文献类型：
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作者：
Yilin Niu;Yue Ding;Hongxin Sheng;Sai Sun;Chaoqin Chen;Jing Du;Hong‐Ying Zang;Peng Yang
半金属含氧阴离子的空间受限组装在[H7 P8 W 48 O 184]33-（P8 W 48）大环内的AsO 33-和SbO 33-，得到了三种纳米聚阴离子[{AsIII 5 O 4（OH）3}2（P8W48O184）]32-（As10），[（SbIIIOH）4（P8 W 48 O 184）]32-（Sb 4）和[（SbIIIOH）8（P8 W 48 O 184）]24-（Sb 8），其结晶为水合混合阳离子盐（Me 2NH 2）13 K7 Na 2Li 10 [{AsIII 5 O 4（OH）3}2（P8W48O184）]·32H2O（DMA-KNaLi-As10）、K20Li12[（SbIIIOH）4（P8W48O184）]·52H2O（KLi-Sb4）和（Me2NH2）8K6Na5Li5[（SbIIIOH）8（P8W48O184）]·65H2O（DMA-KNaLi-Sb8）。大量的固体和溶液状态的物理化学技术被用来系统地表征所制成的化合物的结构和组成。As 10的聚阴离子代表了第一个半金属氧簇取代的P8 W 48的例子，并容纳了迄今为止报道的最大的AsIII-氧簇聚氧乙烯酸盐（POM）。在Sb 4和Sb 8中掺入的SbO 33-基团的数量可以通过含Sb III的前体的简单变化来定制。将半金属含氧阴离子封装在P8 W 48中不仅为POM化学中的主客体组装的开发提供了一种有效的策略，而且还为它们在新兴应用中的功能扩展提供了有效的策略，例如质子传导材料，其中DMA-KNaLi-As 10在85 °C和70%RH下表现出1.2 × 10-2 S cm-1的出色电导率。
Spatially confined assembly of semimetallic oxyanions (AsO33- and SbO33-) within a [H7P8W48O184]33- (P8W48) macrocycle has afforded three nanoscale polyanions, [{AsIII5O4(OH)3}2(P8W48O184)]32- (As10), [(SbIIIOH)4(P8W48O184)]32- (Sb4), and [(SbIIIOH)8(P8W48O184)]24- (Sb8), which were crystallized as the hydrated mixed-cation salts (Me2NH2)13K7Na2Li10[{AsIII5O4(OH)3}2(P8W48O184)]·32H2O (DMA-KNaLi-As10), K20Li12[(SbIIIOH)4(P8W48O184)]·52H2O (KLi-Sb4), and (Me2NH2)8K6Na5Li5[(SbIIIOH)8(P8W48O184)]·65H2O (DMA-KNaLi-Sb8), respectively. A multitude of solid- and solution-state physicochemical techniques were employed to systematically characterize the structure and composition of the as-made compounds. The polyanion of As10 represents the first example of a semimetal-oxo cluster-substituted P8W48 and accommodates the largest AsIII-oxo cluster in polyoxometalates (POMs) reported to date. The number of incorporated SbO33- groups in Sb4 and Sb8 could be customized by a simple variation of SbIII-containing precursors. Encapsulation of semimetallic oxyanions inside P8W48 sets out a valid strategy not only for the development of host-guest assemblies in POM chemistry but also for their function expansion in emerging applications such as proton-conducting materials, for which DMA-KNaLi-As10 showcases an outstanding conductivity of 1.2 × 10-2 S cm-1 at 85 °C and 70% RH.