Two metal−organic frameworks [Zn 2 (Tipa) 2 (OH)]•3NO 3 • 12H 2 O (FIR-53, FIR denotes Fujian Institute of Research, Tipa = tris(4-(1Himidazol-1-yl)phenyl)amine)) and [Zn(Tipa)]•2NO 3 •DMF•4H 2 O) (FIR-54) with large nanotubular channels were synthesized via Zn(II) ions coordinate the neutral Tipa ligand. The framework of FIR-53 contains 1D channels along the c axis with a cross section of 18 × 13 Å 2 . FIR-54 also consists of large channels with the 10.5 × 10.5 Å 2 open windows. These porous materials efficiently trap Cr 2 O 72− inorganic pollutant ions via the single-crystal-to-singlecrystal (SC-SC) approach. The Cr 2 O 7 2− uptake capacities of FIR-53 and FIR-54 are high to 74.2 and 103 mg/g, respectively. Furthermore, the Cr 2 O 7 2− trapping− releasing process of FIR-53 displays good regeneration. Meaningfully, the structure of FIR-53 after ion exchange can be accurately obtained by single-crystal X-ray diffraction, which further elaborates the SC-SC transformation.
Two enantiopure organic ligands integrating flexible proline units and rigid isophthalate units have been rationally designed and employed for the construction of four homochiral porous metal-organic frameworks (MOFs), respectively. One pair of these MOFs is used as heterogeneous catalysts to construct β-lactam derivatives by oxidative coupling reactions.
Homochiral metal-organic frameworks (HMOFs) are efficient materials for enantioselective adsorption. However, the combination of size selectivity and enantioselectivity is still a major challenge in the field of HMOFs. Herein, two enantiomorphic HMOFs built from predesigned proline-derived ligands are presented. Both of them show multiple homochiral features: they contain four different helical chains and three types of helical channels. Due to the size effect of the helical channels, each HMOF can enantioselectively adsorb methyl lactate with high ee. The results reveal a new approach toward size-dependent enantioselective separation of racemic compounds by using HMOFs built from inexpensive proline derivatives.
Utilizing (R)-H3CIA as a chiral template, an unprecedented homochiral metal-organic framework (MOF) with zeotype GIS topology is obtained from achiral 1.4-DIB ligands and Zn(II) ions, which opens up a feasible approach to create zeolitic MOFs with homochirality.
Two three-dimensional (3D) homochiral metal-organic frameworks, integrating double helical chains based on enantiopure ligands and single helical structures braided by 4,4'-bipyridine (bipy) and cadmium clusters, have been synthesized successfully, as a result of complete asymmetric induction between the two types of helix.
Two enantiopure organic linkers ((R)-H 3 CIA and (S)-H 3 CIA) derived from lactic acid have been synthesized and used to construct four pairs of homochiral metal−organic frameworks (HMOFs) with polymetallic building blocks. Crystallographic analysis indicates that H 3 CIA ligands can connect tetranuclear zinc units into kgd type layered structure, whilst the introduction of nitrogen heterocycle auxiliary ligands into this system gives rise to the formation of three-dimensional homochiral MOFs with different structural topologies. Physical characteristics of these complexes are also carried out, including thermal stabilities, solid-state circular dichroism (CD), and photoluminescent properties. Our results highlight the effective method to apply inexpensive and nontoxic chiral ligands to prepare interesting HMOFs.
Eight novel three-dimensional homochiral
helical metal–organic
frameworks (HHMOFs), namely, [Cd3((S)-PIA)2(PPA)(H2O)2]
n
(1-L), [Cd3((R)-PIA)2(PPA)(H2O)2]
n
(1-D), [Cd4((R)-PIA)3(DPP)4(H2O)4]
n
(2-D), [Cd1.5((S)-PIA)(4,4′-DIB)2]
n
(3-L), [Cd1.5((S)-PIA)(DPEE)1.5]
n
(4-L), [Cd1.5((R)-PIA)(DPEE)1.5]
n
(4-D), [Cd1.5((S)-PIA)(DPEA)1.5]
n
(5-L), and [Cd1.5((S)-PIA)(DPEA)1.5]
n
(5-D) (H3PIA = 5-(2-carboxypyrrolidine-1-carbonyl)
isophthalic acid) have been synthesized using proline-derived ligands
((S)-H3PIA and (R)-H3PIA). Crystallographic analysis indicates that all the complexes
contain homochiral left- and/or right-handed helical chains, which
are constructed by PIA fragments and Cd(II) ions. Meanwhile, in these
complexes nitrogen heterocycle auxiliary ligands play an important
role in structural diversity. Some physical characteristics, such
as thermal stabilities, solid-state circular dichroism, and photoluminescent
properties, are also investigated. Our results highlight an effective
method to apply proline ligands to construct interesting HHMOFs.
Presented is a pair of homochiral metal-organic frameworks built from mixed ligands integrating rigid and flexible organic parts, and each compound shows high porosity and can be used for enantioselective separation of racemic 1-phenethylalcohol and methyl lactate.
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