Department of Physical Medicine and Rehabilitation, Sir Run Run Shaw Hospital, Zhejiang University, Hangzhou 310027, P. R. China.
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China.
Sci Adv. 2023 Feb 10;9(6):eade6975. doi: 10.1126/sciadv.ade6975.
Crystalline materials are often considered to have rigid periodic lattices, while soft materials are associated with flexibility and nonperiodicity. The continuous evolution of metal-organic frameworks (MOFs) has erased the boundaries between these two distinct conceptions. Flexibility, disorder, and defects have been found to be abundant in MOF materials with imperfect crystallinity, and their intricate interplay is poorly understood because of the limited strategies for characterizing disordered structures. Here, we apply advanced nuclear magnetic resonance spectroscopy to elucidate the mesoscale structures in a defective MOF with a semicrystalline lattice. We show that engineered defects can tune the degree of lattice flexibility by combining both ordered and disordered compartments. The one-dimensional alignment of correlated defects is the key for the reversible topological transition. The unique matrix is featured with both rigid framework of nanoporosity and flexible linkage of high swellability.
结晶材料通常被认为具有刚性的周期性晶格,而软物质则与柔韧性和非周期性相关。金属-有机框架(MOF)的不断发展已经消除了这两种截然不同概念之间的界限。在结晶度不完善的 MOF 材料中,已经发现了丰富的柔韧性、无序性和缺陷,由于对无序结构的表征策略有限,其复杂的相互作用仍知之甚少。在这里,我们应用先进的核磁共振波谱学来阐明具有半晶格子的有缺陷的 MOF 的介观结构。我们表明,通过组合有序和无序隔室,工程缺陷可以调节晶格柔韧性的程度。相关缺陷的一维排列是可逆拓扑转变的关键。独特的基质具有纳米孔隙的刚性骨架和高溶胀性的柔性连接。