Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Selective gas adsorption and separation in metal–organic frameworks

Metal–Organic Frameworks for Separations

Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long

Carbon Dioxide Capture in Metal–Organic Frameworks

Luminescent Functional Metal–Organic Frameworks

Metal–organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).

Luminescent Metal–Organic Frameworks

Cu2+-Selective Ratiometric and “Off-On” Sensor Based on the Rhodamine Derivative Bearing Pyrene Group

New 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives (1 and 2) were synthesized as an “off−on” fluorescent chemosensor and fluorescent chemodosimeter for Cu2+ and Pb2+. Compound 1 displayed selective and large chelation enhanced fluorescence effects with Pb2+ and Cu2+ among the metal ions examined. On the other hand, compound 2, a fluorescent chemodosimeter, effectively recognized Cu2+ via a selective hydrolysis of the acetyl group.

New BODIPY derivatives as OFF-ON fluorescent chemosensor and fluorescent chemodosimeter for Cu2+: cooperative selectivity enhancement toward Cu2+.

Naphthalimide Modified Rhodamine Derivative: Ratiometric and Selective Fluorescent Sensor for Cu2+ Based on Two Different Approaches

We report a new fluorescent chemosensor that displays an excellent selectivity for pyrophosphate over adenosine triphosphate or phosphate in 100% aqueous solution. A unique fluorescent change was observed upon formation of a 2+2 excimer of the chemosensor.

Pyrophosphate-selective fluorescent chemosensor at physiological pH: formation of a unique excimer upon addition of pyrophosphate.

Therehave been many exciting and significant results from theapplication of new imidazolium receptors to many anionictargets. Martnez-Mez et al. recently reported a colorimet-ric method for the selective determination of anionic surfac-tants using imidazolium-containing ionic liquids on a solidsupport.

Sung Jin Kim

Papers

Cu2+-Selective Ratiometric and “Off-On” Sensor Based on the Rhodamine Derivative Bearing Pyrene Group

New BODIPY derivatives as OFF-ON fluorescent chemosensor and fluorescent chemodosimeter for Cu2+: cooperative selectivity enhancement toward Cu2+.

Naphthalimide Modified Rhodamine Derivative: Ratiometric and Selective Fluorescent Sensor for Cu2+ Based on Two Different Approaches

Pyrophosphate-selective fluorescent chemosensor at physiological pH: formation of a unique excimer upon addition of pyrophosphate.

Thin‐Film Formation of Imidazolium‐Based Conjugated Polydiacetylenes and Their Application for Sensing Anionic Surfactants