Carrington Elliot J, Dodsworth Stephen F, van Meurs Sandra, Warren Mark R, Brammer Lee
Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, S3 7HF, UK.
Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK.
Angew Chem Int Ed Engl. 2021 Aug 9;60(33):17920-17924. doi: 10.1002/anie.202105272. Epub 2021 Jul 12.
Post-synthetic modification (PSM) of the interpenetrated diamondoid metal-organic framework (Me NH )[In(BDC-NH ) ] (BDC-NH =aminobenzenedicarboxylate) SHF-61 proceeds quantitatively in a single-crystal-to-single-crystal manner to yield the acetamide derivative (Me NH )[In(BDC-NHC(O)Me) ] 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.
互穿类金刚石金属有机骨架（Me NH ）[In(BDC-NH ) ]（BDC-NH =氨基苯二甲酸酯）SHF-61的合成后修饰（PSM）以单晶到单晶的方式定量进行，生成乙酰胺衍生物（Me NH ）[In(BDC-NHC(O)Me) ] SHF-62。PSM过程中保留了活化/去溶剂化过程中的连续呼吸行为，但孔闭合现在导致环翻转，以避免修饰配体的酰胺甲基发生空间冲突。这引发了与孔径相关的两个维度上呼吸变形幅度的减小，但与孔长度相关的第三个维度上有大幅增加。MOF从而从主要的二维呼吸（在SHF-61中）转变为明显的三维呼吸运动（在SHF-62中），表明孔宽和孔长呼吸运动的解耦。这些呼吸运动已通过一系列单晶衍射研究进行了测绘。
