Synthesis, Structure, and Properties of a Chiral Zinc(II) Metal-Organic Framework Featuring Linear Trinuclear Secondary Building Blocks

2012 ◽  
Vol 65 (12) ◽  
pp. 1662 ◽  
Author(s):  
Zilu Chen ◽  
Chuanbing Zhang ◽  
Xianlin Liu ◽  
Zhong Zhang ◽  
Fupei Liang

A chiral metal-organic framework formulated as [Zn3(L-TMTA)2(4,4′-bpy)4]·24H2O (1) was prepared from the reaction of Zn(NO3)2·6H2O with trimesoyltri(L-alanine) (L-TMTAH3) in the presence of 4,4′-bipyridine (4,4′-bpy). Compound 1 features linear trinuclear secondary building blocks [Zn3(syn-syn-COO)2(μ2,η3-COO)2]2+. Each linear trinuclear secondary building block is further linked to another eight ones around it by four L-TMTA3– ligands and eight 4,4′-bpy ligands, leading to the construction of a uninodal three-dimensional framework with triangular prism-like one-dimensional channels. Dehydrated compound 1 displays remarkable adsorption selectivity on CO2 and water vapour over N2 gas.

2018 ◽  
Vol 71 (12) ◽  
pp. 978
Author(s):  
Bing Yan ◽  
Huanqiu Li ◽  
Wenyan Jiang ◽  
Long Mu

Targeted anticancer drug delivery systems (DDSs) have been considered as one of the most important approaches for reducing the side effects and enhancing the therapy effect in cancer treatment. This work presents a targeted anticancer DDS on the basis of a newly synthesised adeninate-based metal–organic framework (MOF) [Zn2(ad)2(AMDB)(H2O)](DMF)3 (1) with biomolecular adenine (HAd), zinc(ii) ions, and 4,4′-(aminomethylene)dibenzoic acid (H2AMDB) as the molecular building blocks. The structural analysis via X-ray diffraction technology shows MOF 1 is a channel-type three-dimensional network composed of rod-like Zn–Ad chains. Due to its large inner free spaces and uncoordinated N donor sites functionalised pore surroundings, the antitumour molecule 5-fluorouracil (5-Fu) could be loaded into the pores of 1a (activated 1) though an adsorption process, which shows a moderate high storage capacity of 32 wt-%. At the same time, the pH-dependent delivery of 5-Fu could be achieved in phosphate-buffered saline (PBS) solution. With a lower pH value, the drug release will be enhanced. Furthermore, the invitro antitumour activity of the drug/1a composite has been probed via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay on two human osteogenic sarcoma cells (MG63 and U2OS).


2012 ◽  
Vol 68 (11) ◽  
pp. m306-m308
Author(s):  
Jun-Wei Ye ◽  
Li-Mei Zhao ◽  
Wei Li ◽  
Gui-Ling Ning

In the title cadmium metal–organic framework complex, [Cd(C8H3NO6)(C24H16N2)]nor [Cd(NIPH)(dpphen)] (NIPH is nitroisophthalate and dpphen is 4,7-diphenyl-1,10-phenanthroline), the unique CdIIcation in a general position is coordinated by four carboxy O atoms from three symmetry-related NIPH anions and two N atoms from a dpphen ligand. The CdIIcations are bridged by pairs of NIPH anions to generate a dinuclear molecular building block, [Cd2N4(CO2R)4], with a Cd...Cd separation of 4.0936 (10) Å. Each such building block is connected to four adjacent dinuclear building blocks by NIPH anions, resulting in a two-dimensional layer framework in thebcplane. The dpphen ligands occupy the space between these layers and are linked by π–π interactions, with a separation of 3.4541 (6) Å between the central aromatic rings of inversion-related dpphen ligands. The thermogravimetric and photoluminescent properties of the complex have also been investigated.


2019 ◽  
Vol 5 (5) ◽  
pp. eaav4119 ◽  
Author(s):  
Eunji Jin ◽  
In Seong Lee ◽  
Dongwook Kim ◽  
Hosoowi Lee ◽  
Woo-Dong Jang ◽  
...  

Mechanical metamaterials exhibit unusual properties, such as negative Poisson’s ratio, which are difficult to achieve in conventional materials. Rational design of mechanical metamaterials at the microscale is becoming popular partly because of the advance in three-dimensional printing technologies. However, incorporating movable building blocks inside solids, thereby enabling us to manipulate mechanical movement at the molecular scale, has been a difficult task. Here, we report a metal-organic framework, self-assembled from a porphyrin linker and a new type of Zn-based secondary building unit, serving as a joint in a hinged cube tessellation. Detailed structural analysis and theoretical calculation show that this material is a mechanical metamaterial exhibiting auxetic behavior. This work demonstrates that the topology of the framework and flexible hinges inside the structure are intimately related to the mechanical properties of the material, providing a guideline for the rational design of mechanically responsive metal-organic frameworks.


2017 ◽  
Vol 46 (20) ◽  
pp. 6762-6768 ◽  
Author(s):  
Atsushi Kondo ◽  
Takayuki Suzuki ◽  
Ryosuke Kotani ◽  
Kazuyuki Maeda

A new 3D metal–organic framework (MOF) is reversibly transformed to a 1D chain MOF showing selective adsorption properties.


2019 ◽  
Vol 44 (3-4) ◽  
pp. 193-197
Author(s):  
Xiudian Xu ◽  
Yu Liang ◽  
Junfeng Li ◽  
Lei Zhou ◽  
Li-Zhuang Chen ◽  
...  

A new three-dimensional luminescent cobalt (II) metal–organic framework, [Co(Titpe)(bcpf)·(DMF)]·(H2O)2·(DMF) (compound 1, JUST-8) (Titpe = 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethane, bcpf = 4,4′-sulfonyldibenzoic acid; DMF =  N, N-dimethylformamide), has been solvothermally synthesized by using CoCl2·6H2O and a mixture of ligands: Titpe ligand and bcpf ligand. Single crystal X-ray analysis reveals that 1 crystallizes in the triclinic system and [Formula: see text] space group with a = 13.2097(14) Å, b = 13.9519(14) Å, c = 14.4413(15) Å, α = 89.949(7)°, β = 70.303(7)°, γ = 80.322(7)°, V = 2465.7(5) Å3, Z = 2, Mr =1032.97, Dc = 1.391 g/cm3, μ = 0.455 mm−1, F(000) = 1070, R = 0.0585, and wR = 0.1540 for 8674 observed reflections ( I > 2σ( I)). Its overall structure is a double-fold interpenetrated framework, and it shows a porosity of 12.97% based on a calculation by PLATON and a 4- c type topological network with the point symbol of {6^5.8}. The Co atom bridges the Titpe ligands to form the one-dimensional chains into a two-dimensional layered structure and then connects the auxiliary ligands to get a three-dimensional structure. Compound 1 showed a blue fluorescence emission with the peak maximum at 431 nm (λex = 314 nm).


Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2190
Author(s):  
Jing Chen ◽  
Meng-Yao Chao ◽  
Yan Liu ◽  
Bo-Wei Xu ◽  
Wen-Hua Zhang ◽  
...  

A heterometallic metal−organic framework (MOF) of [Cd6Ca4(BTB)6(HCOO)2(DEF)2(H2O)12]∙DEF∙xSol (1, H3BTB = benzene-1,3,5-tribenzoic acid; DEF = N,N′-diethylformamide; xSol. = undefined solvates within the pore) was prepared by solvothermal reaction of Cd(NO3)2·4H2O, CaO and H3BTB in a mixed solvent of DEF/H2O/HNO3. The compatibility of these two divalent cations from different blocks of the periodic table results in a solid-state structure consisting of an unusual combination of a discrete V-shaped heptanuclear cluster of [Cd2Ca]2Ca′ and an infinite one-dimensional (1D) chain of [Cd2CaCa′]n that are orthogonally linked via a corner-shared Ca2+ ion (denoted as Ca′), giving rise to an unprecedented branched-chain secondary building unit (SBU). These SBUs propagate via tridentate BTB to yield a three-dimensional (3D) structure featuring a corner-truncated P41 helix in MOF 1. This outcome highlights the unique topologies possible via the combination of carefully chosen s- and d-block metal ions with polydentate ligands.


2016 ◽  
Vol 69 (11-13) ◽  
pp. 1792-1801 ◽  
Author(s):  
Xin-Xiong Li ◽  
Kun-Yu Wei ◽  
Ting-Ting Zhuang ◽  
Wei Xia ◽  
Jing-Yu Chen ◽  
...  

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