Post-Synthetic Modification Unlocks a 2D-to-3D Switch in MOF Breathing Response: A Single-Crystal-Diffraction Mapping Study.
Post-Synthetic Modification Unlocks a 2D-to-3D Switch in MOF Breathing Response: A Single-Crystal-Diffraction Mapping Study.
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合成后修饰解锁MOF呼吸反应中的2D到3D转换：单晶衍射映射研究。
DOI：
10.1002/anie.202105272
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发表时间：
2021-08-09
期刊：
影响因子：
--
通讯作者：
Brammer L
中科院分区：
文献类型：
--
作者：
Carrington EJ;Dodsworth SF;van Meurs S;Warren MR;Brammer L
互穿金属有机骨架(Me2NH2)[In(BDC-NH2)2](BDC-NH2=氨基苯二甲酸酯)SHF-61的合成后改性(PSM)以单晶到单晶的方式定量地进行，得到乙酰胺衍生物(Me2NH2)[In(BDC-NHC(O)Me)2]SHF-62。在PSM上保持了活化/去溶过程中的连续呼吸行为，但关闭孔现在会导致环翻转，以避免修饰配体的酰胺甲基的空间碰撞。这引发了与孔径相关的二维呼吸变形幅度的减小，但与孔隙长度相关的第三维呼吸变形幅度的大幅增加。因此，MOF从主要的2D呼吸(在SHF-61中)转换为明显的3D呼吸运动(在SHF-62中)，表明孔宽和孔长呼吸运动的分离。这些呼吸运动已经通过一系列单晶衍射研究得到了映射。类金刚石MOF SHF-61的合成后修饰生成了其甲胺类似物[(Me2NH2)[In(BDC-NH(CO)Me)]，SHF-62为单晶。由此产生的配体空间需求和氢键能力导致MOF呼吸行为的维度从2D呼吸(孔宽)转变为3D呼吸(孔宽和长度)，单晶X射线衍射图显示了这一变化。
Post‐synthetic modification (PSM) of the interpenetrated diamondoid metal–organic framework (Me2NH2)[In(BDC‐NH2)2] (BDC‐NH2=aminobenzenedicarboxylate) SHF‐61 proceeds quantitatively in a single‐crystal‐to‐single‐crystal manner to yield the acetamide derivative (Me2NH2)[In(BDC‐NHC(O)Me)2] SHF‐62. Continuous breathing behaviour during activation/desolvation is retained upon PSM, but pore closing now leads to ring‐flipping to avert steric clash of amide methyl groups of the modified ligands. This triggers a reduction in the amplitude of the breathing deformation in the two dimensions associated with pore diameter, but a large increase in the third dimension associated with pore length. The MOF is thereby converted from predominantly 2D breathing (in SHF‐61) to a distinctly 3D breathing motion (in SHF‐62) indicating a decoupling of the pore‐width and pore‐length breathing motions. These breathing motions have been mapped by a series of single‐crystal diffraction studies. Post‐synthetic modification of diamondoid MOF SHF‐61 generates its methylamide analogue [(Me2NH2)[In(BDC‐NH(CO)Me)], SHF‐62, as single crystals. Resulting ligand steric demands and H‐bonding capability lead to a change in dimensionality of the MOF breathing behaviour from 2D breathing (pore width) to 3D breathing (pore width and length), which has been mapped by single‐crystal X‐ray diffraction.
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