College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , Jiangsu , PR China.
State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032 , PR China.
Inorg Chem. 2018 Jul 16;57(14):8627-8633. doi: 10.1021/acs.inorgchem.8b01408. Epub 2018 Jun 29.
Flexible metal-organic frameworks (MOFs) have attracted great interest for their dynamically structural transformability in response to external stimuli. Herein, we report a switchable "breathing" or "gate-opening" behavior associated with the phase transformation between a narrow pore (np) and a large pore (lp) in a flexible pillared-layered MOF, denoted as MOF-1 as, which is also confirmed by SCXRD and PXRD. The desolvated phase (MOF-1 des) features a unique stepwise adsorption isotherm for N coupled with a pronounced negative gas adsorption pressure. For comparison, however, no appreciable CO adsorption and gate-opening phenomenon with stepwise sorption can be observed. Furthermore, the polar micropore walls decorated with thiophene groups in MOF-1 des reveals the selective sorption of toluene over benzene and p-xylene associated with self-structural adjustment in spite of the markedly similar physicochemical properties of these vapor molecules.
柔性金属-有机骨架（MOFs）因其对外界刺激的动态结构可变性而受到极大关注。在此，我们报道了一种与灵活的支柱层 MOF 中窄孔 (np) 和大孔 (lp) 之间的相转变相关的可切换“呼吸”或“开门”行为，该 MOF 被表示为 MOF-1 as，这也通过 SCXRD 和 PXRD 得到了证实。去溶剂化相 (MOF-1 des) 具有独特的分步吸附等温线，用于 N 耦合，具有明显的负气体吸附压力。然而，相比之下，没有观察到明显的 CO 吸附和分步吸附的开门现象。此外，MOF-1 des 中带有噻吩基团的极性微孔壁显示出对甲苯的选择性吸附，超过了苯和对二甲苯，这与尽管这些蒸气分子具有明显相似的物理化学性质，但仍存在自结构调整。
