Fluorinated metal–organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding of their structure–performance relationships is critical for the synthesis and development of new F-MOFs. This critical review has focused on several strategies for the precise design and synthesis of new F-MOFs with structures tuned for specific gas separation purposes. First, the basic principles and concepts of FMOFs as well as their structure, synthesis and modification and their structure to property relationships are studied. Then, applications of F-MOFs in adsorption and membrane gas separation are discussed. A detailed account of the design and capabilities of F-MOFs for the adsorption of various gases and the governing principles is provided. In addition, the exceptional characteristics of highly stable F-MOFs with engineered pore size and tuned structures are put into perspective to fabricate selective membranes for gas separation. Systematic analysis of the position of F-MOFs in gas separation revealed that F-MOFs are benchmark materials in most of the challenging gas separations. The outlook and future directions of the science and engineering of F-MOFs and their challenges are highlighted to tackle the issues of overcoming the trade-off between capacity/ permeability and selectivity for a serious move towards industrialization.
