Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra.

The chemistry of metal-organic frameworks (MOFs) continues to expand rapidly, providing materials with diverse structures and properties. The reticular chemistry approach, where well-defined structural building blocks are combined together to form crystalline open framework solids, has greatly accelerated the discovery of new and important materials. However, its full potential toward the rational design of MOFs relies on the availability of highly connected building blocks because these greatly reduce the number of possible structures. Toward this, building blocks with connectivity greater than 12 are highly desirable but extremely rare. We report here the discovery of novel 18-connected, trigonal prismatic, ternary building blocks (tbb's) and their assembly into unique MOFs, denoted as Fe-tbb-MOF-x (x: 1, 2, 3), with hierarchical micro- and mesoporosity. The remarkable tbb is an 18-c supertrigonal prism, with three points of extension at each corner, consisting of triangular (3-c) and rectangular (4-c) carboxylate-based organic linkers and trigonal prismatic [Fe3(µ3-Ο)(-COO)6]+ clusters. The tbb's are linked together by an 18-c cluster made of 4-c ligands and a crystallographically distinct Fe3(µ3-Ο) trimer, forming overall a 3-D (3,4,4,6,6)-c five nodal net. The hierarchical, highly porous nature of Fe-tbb-MOF-x (x: 1, 2, 3) was confirmed by recording detailed sorption isotherms of Ar, CH4, and CO2 at 87, 112, and 195 K, respectively, revealing an ultrahigh BET area (4263-4847 m2 g-1) and pore volume (1.95-2.29 cm3 g-1). Because of the observed ultrahigh porosities, the H2 and CH4 storage properties of Fe-tbb-MOF-x were investigated, revealing well-balanced high gravimetric and volumetric deliverable capacities for cryoadsorptive H2 storage (11.6 wt %/41.4 g L-1, 77 K/100 bar-160 K/5 bar), as well as CH4 storage at near ambient temperatures (367 mg g-1/160 cm3 STP cm-3, 5-100 bar at 298 K), placing these materials among the top performing MOFs. The present work opens new directions to apply reticular chemistry for the construction of novel MOFs with tunable porosities based on contracted or expanded tbb analogues.

Reticular Synthesis of Flexible Rare-Earth Metal-Organic Frameworks: Control of Structural Dynamics and Sorption Properties Through Ligand Functionalization.

An exciting direction in metal-organic frameworks involves the design and synthesis of flexible structures which can reversibly adapt their structure when triggered by external stimuli. Controlling the extent and nature of response in such solids is critical in order to develop custom dynamic materials for advanced applications. Towards this, it is highly important to expand the diversity of existing flexible MOFs, generating novel materials and gain an in-depth understanding of the associated dynamic phenomena, eventually unlocking key structure-property relationships. In the present work, we successfully utilized reticular chemistry for the construction of two novel series of highly crystalline, flexible rare-earth MOFs, RE-thc-MOF-2 and RE-teb-MOF-1. Extensive single-crystal to single-crystal structural analyses coupled with detailed gas and vapor sorption studies, shed light onto the unique responsive behavior. The development of these series is related to the reported RE-thc-MOF-1 solids which were found to display a unique continuous breathing and gas-trapping property. The synthesis of RE-thc-MOF-2 and RE-teb-MOF-1 materials represents an important milestone as they provide important insights into the key factors that control the responsive properties of this fascinating family of flexible materials and demonstrates that it is possible to control their dynamic behavior and the associated gas and vapor sorption properties.

A diamino-functionalized silsesquioxane pillared graphene oxide for CO2 capture.

In the race for viable solutions that could slow down carbon emissions and help in meeting the climate change targets a lot of effort is being made towards the development of suitable CO2 adsorbents with high surface area, tunable pore size and surface functionalities that could enhance selective adsorption. Here, we explored the use of silsesquioxane pillared graphene oxide for CO2 capture; we modified silsesquioxane loading and processing parameters in order to obtain pillared structures with nanopores of the tailored size and surface properties to maximize the CO2 sorption capacity. Powder X-ray diffraction, XPS and FTIR spectroscopies, thermal analysis (DTA/TGA), surface area measurements and CO2 adsorption measurements were employed to characterize the materials and evaluate their performance. Through this optimisation process, materials with good CO2 storage capacities of up to 1.7/1.5 mmol g-1 at 273 K/298 K in atmospheric pressure, were achieved.