Five Cd(II) metal–organic frameworks (MOFs), [Cd(HL) 2 ] ( 1 ), [Cd(HL) 2 (H 2 O) 2 ] ( 2 ), [Cd 3 (HL) 2 (obda) 2 ] ( 3 ), [Cd 2 (HL) 2 (ohmbda)(DMA)(H 2 O)] ( 4 ), and [Cd 2 (HL)(btc)(H 2 O) 2 ]·3H 2 O ( 5 ), were prepared by reactions of Cd(NO 3 ) 2 ·4H 2 O with 1-(1 H -imidazol-4-yl)-4-(4 H -tetrazol-5-yl)benzene (H 2 L) or mixed carboxylate ancillary ligands of 1,2-benzenedicarboxylic acid (H 2 obda), 5-hydroxy-1,3-benzenedicarboxylic acid (H 2 ohmbda), and 1,3,5-benzenetricarboxylic acid (H 3 btc), respectively. Their structures have been characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy (IR), thermogravimetric analysis, and powder X-ray diffraction. Compounds 1 and 2 are supramolecular isomeric frameworks without consideration of the solvent molecules. Complex 1 exhibits a binodal (3, 5)-connected two-dimensional (2D) layer structure with the point (Schläfli) symbol of (5 2 ·6)(5 5 ·6 4 ·7), while complex 2 shows a 2D + 2D → 3D (three-dimensional) framework. Complex 3 is a (3, 5, 6)-connected tetranodal 3D net with the point (Schläfli) symbol of (4·8 2 ) 2 (4 5 ·6·8 4 ) 2 (4 5 ·6 5 ) 2 (4 8 ·6 6 ·8). Compound 4 is a (3, 3, 8)-connected trinodal 3D net with the point (Schläfli) symbol based on a binuclear [Cd 2 N 2 O] subunit, while 5 is a 2-nodal (3, 4)-connected 2D V 2 O 5 -type network based on [Cd 2 N 2 (COO) 2 ] SBU. The studies of molecular sensing properties show that the luminescent MOFs can be employed as fluorescent sensors for the detection of Fe 3+ and nitro compounds. Compound 1 and 3 exhibit quenching responses for Fe 3+ in dimethylformamide solution with detection limits of 2.3 × 10 –6 an...
We herein report that the morphology, size, and surface charge status of MIL-100(Fe) micro/nanoparticles can be tailored by adding a coordination modulator (HF or tetramethylammonium hydroxide) to the reaction system. Interestingly, the adsorption capacities of low-crystallinity MIL-100(Fe) and MIL-100(Fe)-TMA toward Congo red (CR) and acid chrome blue K (AC) were found to be significantly larger than that of the high-crystallinity MIL-100(Fe)-HF adsorbent, whereas there was little difference in the adsorption capacities of the three MIL-100(Fe) toward methyl orange (MO) and methylene blue (MB). The adsorption uptake of MIL-100-(Fe)-TMA toward the anionic dyes (CR, AC, and MO) was found to be highest, whereas the adsorption uptake of MIL-100(Fe) toward the cationic dye (MB) was the highest owing to different adsorption mechanisms. This adsorption behavior could be rationalized based on the morphological characteristics and crystal structure defects, zeta potential, and pore volume of MIL-100(Fe) and the adsorption characteristics and molecular structure of the dye. It was revealed that the adsorption performance of MIL-100(Fe) micro/nanoparticles is governed by the synergistic interplay between electrostatic, hydrophobic, and π−π stacking interactions, pore volume, crystal structure defects, and steric hindrance of the adsorbent.
Six metal–organic frameworks of [Cd2(L)2(mmpa)2]·6H2O (1), [Mn2(L)2(mmpa)2]·L·2H2O (2), [Zn(L)(NO2 mbda)]·H2O (3), [Cu(L)(NO2 mbda)] (4), [Co3(L)2(BTC)2(H2O)4]·H2O (5), and [Co3(L)2(OBTC)2(H2O)2] (6) were prepared based on different metal salts and the mixed ligands including the N-heterocyclic 1-(4-(1H-imidazol-5-yl)phenyl)-1H-1,2,4-triazole (L) ligand and auxiliary carboxylic acids of 5-methylisophthalic acid (H2 mmpa), 5-nitroisophthalic acid (H2NO2 mbda), trimesuc acid (H3BTC), and 1,2,3-benzenetricarboxylic acid (H3OBTC). MOFs 1 and 2 are isomorphous and isostructural, and both are binodal 4-connected CdS network based on Cd2(COO)2 binuclear secondary building unit (SBU). Compound 3 is a 2D → 3D “polycatenated network” because of its mutual interpenetration between two-dimensional (2D) corrugated (4, 4) layers, while 4 is a sql network on the basis of binuclear [Cu2(COO)2] SBUs. Compound 5 is a trinodal (3, 4)-connected rare nor-3,4-C2/m 3-fold interpenetrated net, while 6 is a 4-connected 3D frl/Ferey ladder net based on L and two isomers of benzenetricarboxylic acids. Photoluminescent properties were determined for the corresponding d10 MOFs. Microporous crystalline material 1 can selectively sense nitroaromatic compounds by fluorescence quenching and show a rare luminescent sensing property for Ag+ ions in H2O solution. Also, the activated microporous material 1 can selectively adsorb CO2 over N2 and undergo H2O vapor adsorption. Furthermore, magnetostructural analyses have also shown that MOFs 2, 4, 5, and 6 consisting of the paramagnetic ions Mn(II), Cu(II)/Co(II), and carboxylate or N-heterocyclic organic molecules exhibit meaningful magnetic-exchange coupling properties.
Two interpenetrated coordination polymers (CPs) {[Zn1(L)(NO2pbda)]n[Zn2(L)(NO2pbda)]n} (1) and [Zn(L)(Brpbda)]n (2) were prepared by reactions of zinc sulfate heptahydrate with N-donor ligands of 1,4-di(1H-imidazol-4-yl)benzene (L) and auxiliary carboxylic acids of nitroterephthalic acid (H2NO2pbda) and 2,5-dibromoterephthalic acid (H2Brpbda), respectively. The structures of the CPs were characterized by Fourier-Transform Infrared (IR) spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The coordination polymer 1 has two different (4, 4) sql 2D layer structures based on the [Zn(L)(NO2pbda)] moiety, which results in inclined interpenetration with a 2D + 2D → 3D architecture, while the CP 2 exhibits a 3-fold interpenetrating dmp network. The diffuse reflectance spectra are also investigated for the CPs 1 and 2.
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