Hydrolytically Stable Nanoporous Thorium Mixed Phosphite and Pyrophosphate Framework Generated from Redox-Active Ionothermal Reactions

The first thorium
framework compound with mixed-valent phosphorus-based (phosphite and
pyrophosphate) ligands, [BMMim]2­[Th3­(PO3)4­(H2P2O7)3] (ThP-1), was synthesized by ionothermal
reactions concurrent with the partial oxidation of phosphoric acid.
The overall structural topology of ThP-1 highly resembles
that of MOF-5, containing only one type of three-dimensional channels
with a window size of 11.32 Å × 11.32 Å. ThP-1 has a free void volume of 50.8%, making it one of the most porous
purely inorganic actinide-based framework materials. More importantly, ThP-1 is highly stable in aqueous solutions over an extremely
wide pH range from 1 to 14 and thus may find potential applications
in selective ion exchange and catalysis.

首例采用混合价态磷基（亚磷酸和焦磷酸）配体的钍框架化合物[BMMim]2[Th3(PO3)4(H2P2O7)3]（ThP-1）是通过与磷酸部分氧化同时进行的离子热反应合成的。ThP-1的整体结构拓扑结构与MOF-5高度相似，仅含有一种类型的11.32 Å × 11.32 Å窗口尺寸的三维通道。ThP-1具有50.8%的自由空腔体积，使其成为最致密的纯无机锕系框架材料之一。更重要的是，ThP-1在极宽的pH值范围（从1到14）的溶液中表现出极高的稳定性，因此可能在未来在选择性离子交换和催化领域得到潜在应用。