Isopolymolybdate-induced organic–inorganic hybrid assemblies with copper ions and bichelate-bridging ligands

CrystEngComm ◽  
2014 ◽  
Vol 16 (43) ◽  
pp. 10017-10027 ◽  
Author(s):  
Xiu-Li Hao ◽  
Yuan-Yuan Ma ◽  
Yong-Hui Wang ◽  
Hong-Ying Zang ◽  
Yang-Guang Li
Keyword(s):  
Photocatalytic Activity ◽  
Copper Ions ◽  
Bridging Ligands ◽  
Inorganic Hybrid ◽  
Metal Organic ◽  
Hydrothermal Environment ◽  
Hybrid Assemblies

Heptamolybdate is used as a “molecular adaptor” to modulate the metal–organic coordination building units in the hydrothermal environment, with new polyoxometalate-induced hybrid assemblies isolated demonstrating good photocatalytic activity.

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

2019 ◽  
Author(s):  
Andrew Rosen ◽  
M. Rasel Mian ◽  
Timur Islamoglu ◽  
Haoyuan Chen ◽  
Omar Farha ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Screening Methods ◽  
Bridging Ligands ◽  
Metal Centers ◽  
Computational Screening ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O<sub>2</sub> and N<sub>2</sub> adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

scholarly journals 3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis, Crystal Structures, Gas Adsorption, and Magnetic Properties

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1269
Author(s):  
Vadim A. Dubskikh ◽  
Anna A. Lysova ◽  
Denis G. Samsonenko ◽  
Alexander N. Lavrov ◽  
Konstantin A. Kovalenko ◽  
...  
Keyword(s):  
Room Temperature ◽  
Gas Adsorption ◽  
Magnetic Moments ◽  
Bet Surface Area ◽  
Separation Performance ◽  
Bridging Ligands ◽  
Magnetization Data ◽  
Metal Organic ◽  
Ch4 Adsorption ◽  
Gas Separation Performance

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc2−) [Co3(btdc)3(bpy)2]·4DMF, 1; [Co3(btdc)3(pz)(dmf)2]·4DMF·1.5H2O, 2; [Co3(btdc)3(dmf)4]∙2DMF∙2H2O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co3(RCOO)6}, connected either by btdc2– ligands (1, 3) or by both btdc2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N2, O2, CO, CO2, CH4 adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m2⋅g−1 and promising gas separation performance with selectivity factors up to 35.7 for CO2/N2, 45.4 for CO2/O2, 20.8 for CO2/CO, and 4.8 for CO2/CH4. The molar magnetic susceptibilities χp(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μeff (300 K) ≈ 4.93 μB. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2.

Cd(II)-based metal–organic framework-derived CdS photocatalysts for enhancement of photocatalytic activity

2021 ◽  
Vol 56 (14) ◽  
pp. 8643-8657
Author(s):  
Ligang Ma ◽  
Xiaoqian Ai ◽  
Xingming Yang ◽  
Xiaoxiao Cao ◽  
Dianrong Han ◽  
...  
Keyword(s):  
Photocatalytic Activity ◽  
Metal Organic Framework ◽  
Metal Organic ◽  
Organic Framework

scholarly journals Acute Toxicity of Cu-MOF Nanoparticles (nanoHKUST-1) towards Embryos and Adult Zebrafish

2021 ◽  
Vol 22 (11) ◽  
pp. 5568
Author(s):  
Natalia Abramenko ◽  
Gregory Deyko ◽  
Evgeny Abkhalimov ◽  
Vera Isaeva ◽  
Lyubov Pelgunova ◽  
...  
Keyword(s):  
Acute Toxicity ◽  
Toxic Effect ◽  
Biomedical Applications ◽  
Copper Ions ◽  
Adult Zebrafish ◽  
Internal Organs ◽  
Copper Release ◽  
Transmission Electron ◽  
Concentration Dependency ◽  
Metal Organic

Metal-organic frameworks (MOFs) demonstrate unique properties, which are prospective for drug delivery, catalysis, and gas separation, but their biomedical applications might be limited due to their obscure interactions with the environment and humans. It is important to understand their toxic effect on nature before their wide practical application. In this study, HKUST-1 nanoparticles (Cu-nanoMOF, Cu3(btc)2, btc = benzene-1,3,5-tricarboxylate) were synthesized by the microwave (MW)-assisted ionothermal method and characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) techniques. The embryotoxicity and acute toxicity of HKUST-1 towards embryos and adult zebrafish were investigated. To gain a better understanding of the effects of Cu-MOF particles towards Danio rerio (D. rerio) embryos were exposed to HKUST-1 nanoparticles (NPs) and Cu2+ ions (CuSO4). Cu2+ ions showed a higher toxic effect towards fish compared with Cu-MOF NPs for D. rerio. Both forms of fish were sensitive to the presence of HKUST-1 NPs. Estimated LC50 values were 2.132 mg/L and 1.500 mg/L for zebrafish embryos and adults, respectively. During 96 h of exposure, the release of copper ions in a stock solution and accumulation of copper after 96 h were measured in the internal organs of adult fishes. Uptake examination of the major internal organs did not show any concentration dependency. An increase in the number of copper ions in the test medium was found on the first day of exposure. Toxicity was largely restricted to copper release from HKUST-1 nanomaterials structure into solution.

A New Organic-Inorganic Hybrid Based on L-Arginine and Polyoxoanion

2015 ◽  
Vol 1105 ◽  
pp. 335-338
Author(s):  
Qiong Wu ◽  
Jing Lu ◽  
Xiao Lin Ji ◽  
Tao Yu Zou ◽  
Zhen Fang Qiao ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Sodium Cation ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Inorganic Hybrid ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Photocatalytic Activities ◽  
Metal Organic ◽  
Supramolecular Networks

Modifying polyoxometalates with organic and/or metal-organic moieties is a widely adopted method for broading the range of properties. In this work a new polyoxometalate constructed from Anderson-type polyoxoanions and L-arginine (Arg =L-arginine) molecules Na [CrMo6(OH)6O18]}(H2Arg)2·8H2O(1) has been synthesized via conventional method and characterized by routine techniques. Single-crystal X-Ray diffraction analysis shows that compound 1 is constructed by chiralL-arginine grafted Anderson-type clusters, sodium cation and water molecules which are further stabilized by hydrogen bonding interactions constitute 3D supramolecular networks. In addition, both antitumor behavior and photocatalytic activities of compound 1 were investigated.

scholarly journals An organic–inorganic hybrid nanomaterial composed of a Dowson-type (NH4)6P2Mo18O62 heteropolyanion and a metal–organic framework: synthesis, characterization, and application as an effective adsorbent for the removal of organic dyes

RSC Advances ◽  
2020 ◽  
Vol 10 (66) ◽  
pp. 40005-40018
Author(s):  
Akram-Alsadat Hoseini ◽  
Saeed Farhadi ◽  
Abedin Zabardasti ◽  
Firouzeh Siadatnasab
Keyword(s):  
Organic Dyes ◽  
Metal Organic Framework ◽  
Inorganic Hybrid ◽  
Hybrid Nanomaterial ◽  
Metal Organic ◽  
Organic Framework

An MIL-101(Cr) metal–organic framework nanocomposite containing P2Mo18O626− polyanions was prepared and applied as an ultrafast adsorbent to remove organic dyes from water.

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