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Through stepwise post-synthetic spacer insertion and click reactions, six Zr-MOFs with different types and amounts of functional groups have been constructed based on proto-MOF PCN-700. Their gas adsorption capacities and selectivities have been greatly improved and finely tuned, demonstrating the combinatorial effect of pore surface modification and pore space partition. [ABSTRACT FROM AUTHOR]

A 3D porous perchlorinated metal-organic framework (MOF), LIFM-26, featuring dual functionality, that is, functional polar groups and open metal sites, has been synthesized using perchlorinated linear dicarboxylate to link trigonal prismatic Fe3(μ3-O) units. LIFM-26 exhibits good thermal and chemical stability, and possesses high porosity with a BET surface area of 1513 m2 g−1, compared with isoreticular MOF-235 and Fe3O(F4BDC)3(H2O)3 (F4BDC=2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate). Most strikingly, LIFM-26 features good gas sorption/separation performance at 298 K and 1 atm with IAST selectivity values reaching up to 36, 93, 23, 11, 46, and 202 for CO2/CH4, CO2/N2, C2H4/CH4, C2H6/CH4, C3H8/CH4, and R22/N2 (R22=CHClF2), respectively, showing potential for use in biogas/natural gas purification and CO2/R22 capture. [ABSTRACT FROM AUTHOR]

A flexible-robust copper(II) metal-organic framework, denoted as LIFM-100, has been successfully synthesized using a fluorinated linear dicarboxylate to link copper ions. LIFM-100 exhibits a breathing effect, which can transform reversibly between a large form (lp) and a narrow form (np) from single crystal to single crystal. In addition, LIFM-100 shows good thermal and chemical stability. By the introduction of trifluoromethyl functional groups and uncoordinated carboxyl acids, LIFM-100 features a good CO 2 /R22 adsorption/separation performance at 298 K, showing potential in natural gas purification and CO 2 /R22 capture.

Known for excellent stability, porosity and functionality, the high-valent Zr 4+ metal-organic frameworks (Zr-MOFs) still meets synthetic challenge in modulating the strength of Zr-O carboxylate linkage. Herein we explore the unusual coordination dynamics of fluorinated Zr-MOFs by designing two trifluoromethyl modified ligands with distinct geometry preference to form a family of thermodynamic and kinetic products. The low-connecting kinetic Zr-MOFs possess substitutable coordination sites to endow Zr 6 -cluster with extra dynamic behaviors, thus opening a post-synthetic pathway to sequential reassembly/disassembly processes. Comprehensive factors, including ligand geometry, Zr 6 -cluster connectivity, acid modulator and reaction temperature/concentration, have been studied for controllable syntheses. The stability, hydrophobicity and gas adsorption/separation properties of obtained Zr-MOFs are explored. This work sheds light on the understanding of the dynamic coordination chemistry of Zr-MOFs beyond strong Zr-O bond, which poses a versatile platform for modification and functionalization of Zr-MOFs., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Through stepwise post-synthetic spacer insertion and click reactions, six Zr-MOFs with different types and amounts of functional groups have been constructed based on proto-MOF PCN-700. Their gas adsorption capacities and selectivities have been greatly improved and finely tuned, demonstrating the combinatorial effect of pore surface modification and pore space partition.

A 3D porous perchlorinated metal-organic framework (MOF), LIFM-26, featuring dual functionality, that is, functional polar groups and open metal sites, has been synthesized using perchlorinated linear dicarboxylate to link trigonal prismatic Fe 3 (μ 3 -O) units. LIFM-26 exhibits good thermal and chemical stability, and possesses high porosity with a BET surface area of 1513 m 2  g -1 , compared with isoreticular MOF-235 and Fe 3 O(F 4 BDC) 3 (H 2 O) 3 (F 4 BDC=2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate). Most strikingly, LIFM-26 features good gas sorption/separation performance at 298 K and 1 atm with IAST selectivity values reaching up to 36, 93, 23, 11, 46, and 202 for CO 2 /CH 4 , CO 2 /N 2 , C 2 H 4 /CH 4 , C 2 H 6 /CH 4 , C 3 H 8 /CH 4 , and R22/N 2 (R22=CHClF 2 ), respectively, showing potential for use in biogas/natural gas purification and CO 2 /R22 capture., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)