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
复制标题
合成后修饰解锁 MOF 呼吸响应中 2D 到 3D 的转换：单晶衍射图谱研究
DOI：
10.1002/ange.202105272
复制
发表时间：
2021
影响因子：
--
通讯作者：
Carrington E
中科院分区：
文献类型：
--
作者：
Carrington E
互穿类金刚烷金属有机骨架（Me 2NH 2）[In（BDC-NH 2）2]（BDC-NH 2 =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进行，以产生乙酰胺衍生物（Me 2NH 2）[In（BDC-NHC（O）Me）2]SHF-62。在活化/去溶剂化期间的连续呼吸行为在PSM时保留，但是孔闭合现在导致环翻转以避免修饰的配体的酰胺甲基的空间冲突。这引发了在与孔径相关的两个维度上的呼吸变形的幅度的减小，但是在与孔长度相关的第三维度上的大幅增加。因此，MOF从主要的2D呼吸（inSHF-61）转换为明显的3D呼吸运动（inSHF-62），表明孔宽度和孔长度呼吸运动的解耦。这些呼吸运动已经通过一系列单晶衍射研究绘制出来。
Post‐synthetic modification (PSM) of the interpenetrated diamondoid metal–organic framework (Me2NH2)[In(BDC‐NH2)2] (BDC‐NH2=aminobenzenedicarboxylate)SHF‐61proceeds 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 (inSHF‐61) to a distinctly 3D breathing motion (inSHF‐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.