Modulated self-assembly of hcp topology MOFs of Zr/Hf and the extended 4,4'-(ethyne-1,2-diyl)dibenzoate linker
Modulated self-assembly of hcp topology MOFs of Zr/Hf and the extended 4,4'-(ethyne-1,2-diyl)dibenzoate linker
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Zr/Hf 的 hcp 拓扑 MOF 和延伸的 4,4-(乙炔-1,2-二基)二苯甲酸酯连接体的调制自组装
DOI：
10.1039/d2ce01529c
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发表时间：
2023
期刊：
影响因子：
3.1
通讯作者：
Boyadjieva S
中科院分区：
文献类型：
--
作者：
Boyadjieva S
仔细控制合成条件可以增强单个金属-连接体组合中金属有机框架（MOF）的结构多样性。在此，我们表明，Zr(IV) 和 Hf(IV) 的 hcp 拓扑 MOF 通过延伸的 (1,2-二基)二苯甲酸酯连接体连接，可以通过调节自组装来制备。溶剂热合成中乙酸和水的受控添加对于生成这些相纯 hcp 拓扑材料至关重要，这些材料通过实验和计算进行表征。连接子的中心炔单元可以定量溴化，但这会导致 hcp 相部分降解，与更稳定的 fcu 拓扑类似物相比。尽管如此，MOF 代表了 hcp 拓扑等网状系列的新成员，具有高结晶度和孔隙率，并表明通过明智地调整关键合成参数可以在现有 MOF 相空间中发现新材料。
Careful control of synthetic conditions can enhance the structural diversity of metal–organic frameworks (MOFs) within individual metal-linker combinations. Herein, we show that hcp topology MOFs of both Zr(IV) and Hf(IV), linked by the extended (ethyne-1,2-diyl)dibenzoate linker, can be prepared by modulated self-assembly. The controlled addition of acetic acid and water to solvothermal syntheses is essential to generate these phase pure hcp topology materials, which are characterised experimentally and computationally. The central alkyne unit of the linker can be quantitatively brominated, but this results in partial degradation of the hcp phase, in contrast to the more stable fcu topology analogues. Nevertheless, the MOFs represent new members of the hcp topology isoreticular series showing high crystallinity and porosity, and demonstrate that new materials can be discovered in existing MOF phase spaces through judicious adjustment of key synthetic parameters.