In this work a family of multidimensional (2‐(1H‐tetrazol‐5‐yl)ethyl) amino acid coordination compounds have been synthesized and thoroughly characterized. For this purpose, glycine, valine, ...phenylalanine and tyrosine have been selected as starting amino acids and Mn2+, Zn2+ and Cd2+ as metallic nodes. From one side, for Mn2+ based dimer magnetic resonance imaging studies have been conducted, prompted by the number and disposition of the coordinated water molecules and taking into consideration the promising future of manganese‐based coordination compounds as bio‐compatible substitutes to conventional Gd based contrast agents. From another side, d10 block metal‐based complexes allowed exploring photoluminescence properties derived by in situ synthesized ligands. Finally, amino acid preserved structural chirality allowed us to examine chiroptical properties, particularly focusing on circularly polarized luminescence.
A family of multidimensional coordination compounds have been synthesized based on glycine, valine, phenylalanine and tyrosine. Magnetic resonance imaging studies and chiroptical properties have been explored.
Solvothermally promoted assembly of the multifunctional 3‐amino‐4‐hydroxybenzoic acid ligand with the corresponding Eu salt gives rise to the formation of a porous metal‐organic framework with the ...general formula {Eu5L6(OH)3(H2O)3 ⋅ 5DMF}n (1) that has been tested as heterogeneous catalyst for the cyanosilylation of a broad scope of ketones in solvent‐free conditions, using the lowest catalyst loading of 0.5 mol% ever reported, and exhibiting no leak and high recyclability.
MOF for cyanosilylation: A new Europium MOF has been synthesized, characterized and its electrophoretic and catalytic behavior thoroughly studied. The new MOF system has demonstrated a negative surface charge at basic conditions that in the cyanosilylation of ketones (17 examples) and aldehydes (3 examples) afforded outstanding catalytic performance using the most reduced catalyst loading described in the literature and full recyclability at least during the first seven cycles.
As a starting point, a new 3D porous framework with the {CoL·0.5DMF·H
O}
chemical formula (where L = 3-amino-4-hydroxybenzoate) is described. Its performance as a single molecule magnet was explored. ...The study of magnetic properties reveals that Co-MOF shows no frequency-fdependant alternating current (
) signals under zero direct current (
) magnetic field, whereas single-molecule magnet behaviour is achieved when Co
ions are diluted in a Zn
based matrix. Interestingly, this strategy renders a bifunctional Co
Zn
L
material that is also characterized by a strong photoluminescent emitting capacity.
Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) ...are promising materials for combating them effectively. Herein, a novel Cu-MOF-namely
-that displays the formula Cu
L
(DMF)
(DMF =
,
-dimethylformamide) is described, synthesized by the combination of copper(II) and 3,4-dihydroxybenzoic acid (H
L)-both having well-known antibacterial properties. The resulting three-dimensional structure motivated us to study the antibacterial activity, adsorptive capacity and processability of the MOF in the form of pellets and membranes as a proof-of-concept to evaluate its future application in devices.
Herein, to the best of our knowledge, the first heterobimetallic Y/Eu porous metal–organic framework (MOF), based on 3-amino-4-hydroxybenzoic acid (H2L) ligand, with the following formulae ...{Y3.5Eu1.5L6(OH)3(H2O)3·12DMF}n (in advance, namely Y/Eu-MOF), is described. The three-dimensional structure has been synthesized by solvothermal routes and thoroughly characterized, by means of single crystal X-ray diffraction, powder X-ray diffraction, electronic microscopy, ICP-AES, electrophoretic mobility, and FTIR spectra. Intriguingly, the porous nature allows for coordinated solvent molecules displacement, yielding unsaturated metal centers, which can act as a Lewis acid catalyst. This novel supramolecular entity has been tested in cyanosilylation and hydroboration reactions on carbonyl substrates of a diverse nature, exhibiting an extraordinary activity.
Konposatu metal-organikoen propietate interesgarriak direla eta, azken hiru hamarkadetan material horien ikerketak iraultza handia izan du. Ikerketa-taldeek zein industriak jarri ditu MOFen aplikazio ...posibleak ikerketaren jomugan. Horregatik, laborategitik industria-mailako ekoizpenera igarotzeko modua ikertzea oso garrantzitsua da ehungintzan eta garraiobideen eta elikagaien industrian. Testuinguru horretan, artikulu honek laborategi-mailako sintesitik industriako ekoizpen handiko sintesira igarotzeko kontuan hartu beharreko faktoreak argitu eta eskala handian produzitutako MOFen lehen aplikazioak aurkeztu nahi ditu.
A three-dimensional heterobimetallic porous structure with the formula {Y3.5Tb1.5L6(OH)3(H2O)1.5 (DMF)1.5 n ·1.5H2O·DMF} n (L = 3-amino-4-hydroxybenzoate) (Y/Tb-MOF) has been synthesized and ...characterized by single crystal and powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), inductively coupled plasma mass spectrometry (ICP-MS), electrophoretic mobility, and Fourier transform infrared (FTIR) spectroscopy. The structure presents two metal environments: a bioaugmented isosceles wedge (mm2) MO8 and a tricapped trigonal prism (−6m2) MN3O6. These configurations facilitate the creation of channels with a diameter of 10.7 Å, enabling its utilization as an active catalyst where the heterobimetallic nature of the assembly will be explored. This mixed-metal metal–organic framework has been tested in the cycloaddition of epoxides with carbon dioxide as well as in the cyanosilylation and hydroboration reactions of carbonylic substrates. Additionally, a monometallic Tb-MOF analogue has been synthesized for comparative evaluation of their catalytic performances. Both the mixed metal and monometallic variants exhibit outstanding activity in the cyanosilylation and hydroboration of carbonyls and in the synthesis of carbonates under CO2 pressure. However, only the latter exhibits high recyclability.
The development of convenient, non-complicated, and cost-efficient processing techniques for packing low-density MOF powders for industry implementation is essential nowadays. To increase MOFs’ ...availability in industrial settings, we propose the synthesis of a novel 3D Tb-MOF (1) and a simple and non-expensive method for its immobilization in the form of pellets and membranes in polymethacrylate (PMMA) and polysulphone (PSF). The photoluminescent properties of the processed materials were investigated. To simulate industrial conditions, stability towards temperature and humidity have been explored in the pelletized material. Water-adsorption studies have been carried out in bulk and processed materials, and because of the considerable capacity to adsorb water, proton-conduction studies have been investigated for 1.
Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae Zn(L)(H2O)n (1) and Cd2(HL)4n (2) have been synthesized and fully ...characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds.
New dinuclear MII-LnIII complexes of general formulas Cu(µ-L)(µ-OAc)Ln(NO3)2·CH3CN·H2O (LnIII = Gd (1), Tb (2), Dy (3) and Er (4)), Ni(CH3CN)(µ-L)(µ-OAc)Ln(NO3)2·CH3CN (LnIII = Nd (5), Gd (6), Tb ...(7), Dy (8), Er (9) and Y (10)) and Co(CH3CN)(µ-L)(µ-OAc)Ln(NO3)2·CH3CN (LnIII = Gd (11), Tb (12), Dy (13), Er (14) and Y (15)) were prepared from the compartmental ligand N,N′-dimethyl-N,N′-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the transition metal ions occupy the internal N2O2 coordination site of the ligand, whereas the LnIII ions lie in the O4 external site. Both metallic ions are connected by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged MIILnIII compounds. Direct current (dc) magnetic measurements allow the study of the magnetic exchange interactions between the 3d and 4f metal ions, which is supported by density functional theory (DFT) theoretical calculations for the GdIII-based counterparts. Due to the weak ferromagnetic exchange coupling constants obtained both experimentally and theoretically, the magneto-thermal properties of the less anisotropic systems (compounds 1 and 6) are also studied. Alternating current (ac)magnetic measurements reveal the occurrence of slight frequency dependency of the out-of-phase signal for complexes 8, 9 and 13, while complex 15 displays well-defined maximums below ~6 K.
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