Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework.
Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework.
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MIL-53拓扑金属-有机骨架中压力诱导的后合成团簇阴离子取代。
DOI：
10.1039/d3sc00904a
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发表时间：
2023-07-19
期刊：
影响因子：
8.4
通讯作者：
中科院分区：
文献类型：
--
作者：
金属有机框架（MOF）的合成后修饰已被证明是一种非常强大的工具，可以通过利用MOF连接体及其无机二级结构单元（SBU）上的反应位点来调节物理性质并引入功能，因此促进了广泛的应用。对MOF SBU的反应性的研究仅集中在中性配位溶剂的去除或连接体如羧酸酯的直接交换上，尽管在许多SBU中发现辅助电荷平衡氧化物和氢氧化物配体的流行。在本文中，我们表明MIL-53拓扑结构Sc MOF，GUF-1中的μ2-OH配体是不稳定的，并且可以通过与孔结合的甲醇分子反应来取代μ2-OCH 3单元，这是一个非常罕见的压力诱导的合成后修饰的例子。使用全面的固态NMR光谱分析，我们显示了一个数量级的增加，在这个簇阴离子取代过程后，暴露在甲醇中悬浮的大体积样品的压力为0.8 GPa在一个大体积的压力。此外，在金刚石对顶砧单元中用甲醇作为压力传递介质压缩的单晶已经能够在一系列压力下对该过程进行完整的结构表征，从而在4.98 GPa下定量地将单晶转化为单晶。这种意想不到的SBU反应性（在这种情况下是甲醇的化学吸附）对一系列MOF化学具有影响，从非均相催化的小分子活化到化学稳定性，我们预计簇阴离子取代将发展成为一种非常方便的新型方法用于修饰一系列多孔材料的内部孔表面和化学性质。压力的应用诱导孔结合的甲醇与金属有机框架GUF-1（Sc）的二级结构单元的反应性，取代协调的桥接氢氧化物配体桥接甲醇盐，在单晶和散装。
Postsynthetic modification of metal–organic frameworks (MOFs) has proven to be a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the μ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for μ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity – in this case chemisorption of methanol – has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials. Application of pressure induces reactivity of pore-bound methanol with the secondary building unit of the metal–organic framework GUF-1(Sc), substituting coordinated bridging hydroxide ligands for bridging methoxides, in single crystals and in bulk.
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影响因子：
18.2
作者：
Brozek CK;Michaelis VK;Ong TC;Bellarosa L;López N;Griffin RG;Dincă M
通讯作者：
Dincă M
影响因子：
15
作者：
Burnett, Brandon J.;Barron, Paul M.;Choe, Wonyoung
通讯作者：
Choe, Wonyoung
影响因子：
9.5
作者：
Bae, Jinhee;Choi, Jae Sun;Jeong, Nak Cheon
通讯作者：
Jeong, Nak Cheon
影响因子：
13.3
作者：
Bara D;Meekel EG;Pakamorė I;Wilson C;Ling S;Forgan RS
通讯作者：
Forgan RS
影响因子：
3.7
作者：
Boutin, Anne;Bousquet, David;Patarin, Joel
通讯作者：
Patarin, Joel