Highly selective separation and/or purification of acetylene from various gas mixtures is a relevant and difficult challenge that currently requires costly and energy-intensive chemisorption processes. Two ultramicroporous metal-organic framework physisorbents, NKMOF-1-M (M=Cu or Ni), offer high hydrolytic stability and benchmark selectivity towards acetylene versus several gases at ambient temperature. The performance of NKMOF-1-M is attributed to their exceptional acetylene binding affinity as revealed by modelling and several experimental studies: in situ single-crystal X-ray diffraction, FTIR, and gas mixture breakthrough tests. NKMOF-1-M exhibit better low-pressure uptake than existing physisorbents and possesses the highest selectivities yet reported for C H /CO and C H /CH . The performance of NKMOF-1-M is not driven by the same mechanism as current benchmark physisorbents that rely on pore walls lined by inorganic anions.
A molecular spring formed by a hydrophobic metal-organic framework Cu (tebpz) (tebpz=3,3',5,5'-tetraethyl-4,4'-bipyrazolate) and water is presented. This nanoporous heterogeneous lyophobic system (HLS) has exceptional properties compared to numerous reported systems of such type in terms of stability, efficiency, and operating pressure. Mechanical and thermal energetic characteristics as well as stability of the system are discussed and compared in detail with those of other previously reported HLS.
The
corrole unit from the porphyrinoid family represents one of
the most important ligands in the field of coordination chemistry,
which creates a unique environment allowing for the observation of
unusual electronic states of bound metal cations and has shown great
promise in various applications. Nevertheless, studies that directly
and systematically introduce these motifs in porous crystalline materials
for targeting further functionalizations are still lacking. Herein,
we report for the first time the construction of two robust corrole-based
metal–organic frameworks (MOFs), M6(μ3-O)4(μ3-OH)4(OH)3(H2O)3(H3TCPC)3 (M = Zr for Corrole-MOF-1 and M = Hf for Corrole-MOF-2, H3TCPC = 5,10,15-tris(p-carboxylphenyl)corrole), which are assembled by a custom-designed C
2ν
-symmetric corrolic
tricarboxylate ligand and the unprecedented D
3d
-symmetric 9-connected Zr6/Hf6 clusters. The resultant frameworks feature a rare (3,9)-connected gfy net and exhibit high chemical stability in aqueous solutions
within a wide range of pH values. Furthermore, we successfully prepared
the cationic Corrole-MOF-1(Fe) from the iron corrole
ligand, which can serve as an efficient heterogeneous catalyst for
[4 + 2] hetero-Diels–Alder reactions between unactivated aldehydes
and a simple diene, outperforming both the homogeneous counterpart
and the porphyrinic MOF counterpart.
Herein, for the first time, we present the successful synthesis of a novel two‐dimensional corrole‐based covalent organic framework (COF) by reacting the unusual approximately T‐shaped 5,10,15‐tris(p‐aminophenyl)corrole H3TPAPC with terephthalaldehyde, which adopts desymmetrized hcb topology and consists of a staggered AB stacking structure with elliptical pores. The resultant corrole‐based COF, TPAPC‐COF, exhibits high crystallinity and excellent chemical stability. The combination of extended π‐conjugated backbone and interlayer noncovalent π–π interactions endows TPAPC‐COF with excellent absorption capability in the entire visible‐light and even near‐infrared regions. Moreover, this work suggests the promise of TPAPC‐COF as a new class of photoactive material for efficient singlet‐oxygen generation with potential photodynamic therapy application as demonstrated by in vitro anticancer studies.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.