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Molecular Retrofitting Adapts a Metal–OrganicFramework to Extreme Pressure

机译:分子改造可适应金属有机物承受极端压力的框架

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摘要

Despite numerous studies on chemical and thermal stability of metal–organic frameworks (MOFs), mechanical stability remains largely undeveloped. To date, no strategy exists to control the mechanical deformation of MOFs under ultrahigh pressure. Here, we show that the mechanically unstable MOF-520 can be retrofitted by precise placement of a rigid 4,4′-biphenyldicarboxylate (BPDC) linker as a “girder” to afford a mechanically robust framework: MOF-520-BPDC. This retrofitting alters how the structure deforms under ultrahigh pressure and thus leads to a drastic enhancement of its mechanical robustness. While in the parent MOF-520 the pressure transmitting medium molecules diffuse into the pore and expand the structure from the inside upon compression, the girder in the new retrofitted MOF-520-BPDC prevents the framework from expansion by linking two adjacent secondary building units together. As a result, the modified MOF is stable under hydrostatic compression in a diamond-anvil cell up to 5.5 gigapascal. The increased mechanical stability of MOF-520-BPDC prohibits the typical amorphization observedfor MOFs in this pressure range. Direct correlation between the orientationof these girders within the framework and its linear strain was estimated,providing new insights for the design of MOFs with optimized mechanicalproperties.
机译:尽管对金属有机骨架(MOF)的化学和热稳定性进行了大量研究,但机械稳定性仍未得到广泛发展。迄今为止,还没有策略可以控制MOF在超高压下的机械变形。在这里,我们显示出机械上不稳定的MOF-520可以通过将刚性4,4'-联苯二甲酸(BPDC)接头作为“大梁”的精确放置进行改装,以提供机械坚固的框架:MOF-520-BPDC。这种改型改变了结构在超高压下的变形方式,从而大大增强了其机械强度。在母体MOF-520中,压力传递介质分子扩散到孔中并在压缩时从内部扩展结构,而新改装的MOF-520-BPDC中的大梁则通过将两个相邻的二级建筑单元连接在一起来防止框架扩展。结果,改性的MOF在静压压缩下在高达5.5吉帕斯卡的金刚石-砧座中是稳定的。 MOF-520-BPDC增强的机械稳定性阻止了观察到的典型非晶化在此压力范围内的MOF。方向之间直接相关框架中的这些大梁及其线性应变,通过优化机械性能为MOF设计提供新见解属性。

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