Highly porous and robust ionic MOFs with nia topology constructed by connecting an octahedral ligand and a trigonal prismatic metal cluster

Abstract

Two non-interpenetrated and isomorphous MOFs with nia topology, cationic JUC-101 and anionic JUC-102, are synthesized by connecting a trigonal prismatic metal cluster with an octahedral organic ligand. JUC-101 obtains a BET surface area of 3742 m(2) g(-1) and can absorb 4.18 wt% of H2 at 30 atm and 77 K, while JUC-102 can absorb cationic dye molecules and release them under the triggering of ions.

Cobalt(II)–Lanthanide(III) Heterometallic Metal–Organic Frameworks with Unique (6,6)‐Connected Nia Topologies with 1H‐1,2,3‐Triazole‐4,5‐dicarboxylic Acid: Syntheses, Structures and Magnetic Properties

“…As shown in Figure 4, the χ M T values observed at room temperature are 9.53 (Co-Eu), 15 As the samples were cooled, the χ M T values decrease monotonously, reaching a minimum of 0.342 (Co-Eu), 8.01 (Co-Gd), 6.97 (Co-Tb), and 9.94 cm 3 K mol -1 (Co-Dy) at 2 K. The χ M T values decrease with decreasing temperature, possibly as a result of antiferromagnetic interactions or spin-orbit coupling and crystal-field effects. [18] The χ M T values are not zero at 2 K, which indicates the population of the paramagnetic states due to a very weak exchange involving the lanthanide(III) ions.…”

“…To confirm their thermal stabilities, TGA was also performed under N 2 (Figure S2). The TGA curves show that the weight losses of the four isostructural Co-Ln heterometallic MOFs below 250°C are analogous and correspond to the removal of two uncoordinated water molecules and three-quarters of a dmf molecule (found: 7.55 % for Co-Eu, 8.73 % for Co-Gd, 8.68 % for Co-Tb, 8.48 % for Co-Dy; calcd. : 7.86 % for CoEu, 7.82 % for Co-Gd, 7.81 % for Co-Tb, 7.79 % for Co-Dy).…”

“…The former has been achieved in {[Zn 4 O(tta)(dma) 2 ]·3dma·21H 2 O} n {H 6 tta = 4,4Ј,4ЈЈ-tris[N,NЈ-bis(4-carboxyphenyl)amino]triphenylamine}, [7] and the latter can be observed in {[In 3 O-(tdcpb)(H 2 O) 3 ] (xGuest)} n and {[Mn 3 (OH)(tdcpb)(H 2 O) 3 ] (xGuest)} n {tdcpb = 1,3,5-tris[3,5-bis(4-carboxyphenyl)-phenyl]benzene}. [8] However, it is quite a challenge to simultaneously assemble two such different nodes into a singular system because of the difficulty in obtaining such a specific geometry of the binodal nodes. As a result, the nia topology is still rare in MOF chemistry.…”

“…[16] Notably, such (6,6)-connected nia nets are still rare for MOF materials; to the best of our knowledge, only a few examples can be found in the recent literature. [7][8][9] However, these known nia nets are homometallic MOFs and no 3d-4f heterometallic MOFs with (6,6)-connected nia topology have been reported to date. In contrast to the known nia topological structures, these 3d-4f nia topologies have been realized neither by connecting trigonal prismatic OBBs with octahedral IBBs nor trigonal prismatic IBBs with octahedral OBBs.…”

“…As a result, the nia topology is still rare in MOF chemistry. [7][8][9] On the other hand, 3d-4f heterometallic metal-organic frameworks are one such type of attractive MOF in which transition-metal and lanthanide ions are incorporated into a system simultaneously. Combinations of transition-metal and lanthanide ions in a single MOF have great potential in the field of functional crystalline materials that cannot be realized by individual 3d or 4f metal ions.…”