Diisophthalic Acid Research Articles

A porous metal-organic framework based on an asymmetric angular diisophthalate for selective adsorption of C2H2 and CO2 over CH4.

A new copper-based metal-organic framework [Cu2L(H2O)2]·5DMF·2H2O (ZJNU-56) has been solvothermally synthesized using a custom-designed asymmetric rigid bent diisophthalate ligand, 5,5'-(1-amine-naphthyl-2,4-diyl) diisophthalic acid (H4L), and structurally determined by single-crystal X-ray diffraction. ZJNU-56 features a three-dimensional (3D) open framework incorporating three different types of metal-organic cages and two distinct types of one-dimensional channels. With a moderate BET surface area of 1655 m2 g-1, optimized pore structure, and functional sites (open copper sites and Lewis basic amine groups) on the cage surface, ZJNU-56 after desolvation exhibits highly selectively adsorptive separation of C2H2 and CO2 over CH4 under ambient conditions. At 298 K, the predicted IAST selectivities are 35.7-72.9 for an equimolar C2H2/CH4 gas mixture and 6.8-7.0 for an equimolar CO2/CH4 gas mixture at pressures varying from 1 to 109 kPa, respectively, which are among the highest reported to date for copper-based MOFs.

A novel methoxy-decorated metal–organic framework exhibiting high acetylene and carbon dioxide storage capacities

A methoxy-decorated novel metal–organic framework (MOF), Cu2(DTPD) (ZJU-12, H4DTPD = 5,5′-(2,6-dimethoxynaphthalene-1,5-diyl)diisophthalic acid) with optimized pore space and open metal sites, was solvothermally synthesized and structurally characterized. The activated ZJU-12a displays a moderately high BET (Brunauer–Emmett–Teller) surface area of 2316 m2 g−1. Due to the pore size of the crystal being consistent with the molecular size and kinetic diameters of C2H2 and CO2, ZJU-12a exhibits a high C2H2 storage capacity of 244 cm3 g−1 and CO2 capture capacity of 134 cm3 g−1 at room temperature.

Synthesis, luminescent sensing based on a three-fold interpenetrating network with flexible carboxylates

A Zn-based complexes with chemical formulae {[Zn(L)0.5(4,4'-Bipy)] · 2H2O} (I) (H4L = 5,5'-(1,4-phenylene-bis(methylene))bis(oxy) diisophthalic acid), has been synthesized and structurally characterized. Single-crystal X-ray crystallography (CIF file CCDC no. 1465538) reveals that compound I shows a three-dimensional three-fold interpenetrating network simplified by a bbf topology (vertex symbol (66)2(64.82)). Complex I can work as highly sensitive sensors to Cu2+, CrO 4 2- and explosive by luminescent quenching.

High CO2 Uptake Capacity and Selectivity in a Fascinating Nanotube-Based Metal–Organic Framework

An unusual porous metal-organic framework has been synthesized by using Pb(II) and rigid V-shaped 4,4'-(pyridine-3,5-diyl)diisophthalic acid (H4L). Structure analysis reveals that there exist 1D cylindrical 14.26 Å and triangular prism 10.69 × 10.69 × 10.69 Å3 nanotubes in the framework. Gas sorption behavior of the nanoporous MOF shows a relatively high capacity and selectivity of CO2 over CH4.

A fluorescent lanthanide-organic framework for highly sensitive detection of nitroaromatic explosives

A lanthanide-organic framework constructed from a new π-electron rich ligand 5,5′-(9H-carbazole-3,6-diyl)diisophthalic acid (H4L) and Tb(NO3)3·6H2O, namely, [(CH3)2NH2][TbL] (1), has been synthesized under solvothermal condition. X-ray diffraction analysis reveals that complex 1 exhibits a 3D porous framework featuring a (4,8)-connected sqc net. The solid sample of 1 exhibits strong green fluorescence in the visible region upon excitation at 354nm. The fine grinding particles of 1 dispersed in ethanol shows good sensitivity for picric acid (PA), which can be reused at least five times for detecting PA. The good sensitivity and recyclability of 1 make it a potential fluorescent sensor for explosives detection.

Two Functional Porous Metal–Organic Frameworks Constructed from Expanded Tetracarboxylates for Gas Adsorption and Organosulfurs Removal

Two fof-type porous metal–organic frameworks (MOFs), [Cu2(bdfdpa)(H2O)2]·8DMF·2H2O (JLU-Liu29) and [Cu2(btadpa)(H2O)2]·7DMF·8H2O (JLU-Liu30) (H4bdfdpa = 5,5′-(benzo[1,2-b:4,5-b′]difuran-2,6-diyl)diisophthalic acid and H4btadpa = 5,5′-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-diyl))diisophthalic acid), have been successfully synthesized by using different expanded tetracarboxylate ligands. Both of them exhibit good permanent porosity and high surface areas of 2205 and 1791 m2 g–1, respectively. Due to open metal sites, different functional groups, and suitable pore spaces, the two porous MOFs exhibit high adsorption performance for small molecule gases (CO2, CH4, C2H6, and C3H8) and removal of refractory organosulfur compounds.

Mechanically Robust Hybrid Hydrogels for Photovoltaic Applications

SummaryConducting dihybrid(GP), trihybrid(GPPS) hydrogels have been constructed using 5,5'‐(1,3,5,7‐tetraoxopyrrolo[3,4‐f]isoindole‐2,6‐diyl) diisophthalic acid (P), graphene oxide(GO,G) and PEDOT:PSS(PS). These gels are well characterised by SEM, TEM, rheology, FTIR and Raman Spectroscopy. GP hybrid gels display higher mechanical stability, compared to the P gel. GPPS trihybrid gels shows dc‐conductivity up to 0.011 Scm−1. In gel state it shows rectification property with a highest rectification ratio of 61; however, the xerogels exhibit semiconducting nature. Dye sensitized solar cells (DSSCs) are engineered using the GPPS gels as active materials and exhibit a maximum power conversion efficiency of 4.46%.

Synthesis of a 3-D porous Tb-MOF: organic dye adsorption

A 3-D lanthanide metal–organic framework, [Tb2(L)1.5(DMF)2]·2DMF (1) (L = 14-diylbis(acylamino-21-diyl))-diisophthalic acid), has been synthesized under solvothermal conditions. 1 was characterized by X-ray single-crystal analysis and powder X-ray diffraction. The 3-D framework of 1 is constructed by 2-D channels embedded in a plane. Network analysis reveals that 1 is a (4,5,6,6)-connected net with stoichiometry (4-c)2(5-c)2(6-c)3. As expected, this terbium(III) metal–organic framework exhibits good properties for adsorbing organic dye molecules due to its NH- group. It shows good adsorption selectivity for rhodamine B (RB) rather than methyl orange (MO) and methylene blue (MB) molecules.

A Highly Chemically Stable Metal–Organic Framework as a Luminescent Probe for the Regenerable Ratiometric Sensing of pH

A heteroatom-rich 3D noninterpenetrating metal-organic framework (MOF) Cd-EDDA constructed from an ethylene glycol ether bridging tetracarboxylate ligand H4 EDDA (5,5'-(ethane-1,2-diylbis(oxy))diisophthalic acid) shows good chemical resistance to both acidic and alkaline solutions with a pH ranging from 2.0 to 12.2. There is a corresponding ratiometric luminescence response to pH from 2.0 to 11.5, and the sensing mechanism is also discussed through ion chromatography and molecular force field-based calculations. Importantly, the probe can easily be regenerated simply by modulating the pH of the solution, thus being the first example of a regenerable MOF-based ratiometric luminescent probe for pH.

A new double layered 2-D copper(II) coordination polymer based on a semi-rigid ligand

A new 2-D Cu(II) coordination polymer, [Cu2(L)(H2O)3]·4.5H2O (1) [H4L = 5,5′-(pyrazine-2,3-diylbis(azanediyl))diisophthalic acid], has been synthesized from the reaction of Cu(NO3)2·3H2O with H4L under solvothermal conditions. H4L was prepared and characterized by 1H NMR, 13C NMR, elemental analysis (EA), and infrared spectroscopy (IR). X-ray single-crystal diffraction analysis reveals that 1 crystallized in the hexagonal space group P6522 with a = 16.318(1), b = 16.318(1), c = 35.632(6) Å, V = 8217.0(8) Å3, Z = 12 and afforded 2-D grid-like double layers with a [3,5] topology network. The staggered arrangement of the 2-D layers afforded a dense structure through H-bonds. Further characterizations for 1 were performed by powder X-ray diffraction, thermogravimetric analysis, EA, IR, etc. Magnetic measurements revealed antiferromagnetic interactions between the adjacent Cu(II) centers within 1.

A new luminescent metal-organic framework for selective sensing of nitroaromatic explosives

A microporous luminescent metal-organic framework [Zn4L2(H2O)2]·(H2O) m (DMA) n ( 1 ) (H4L=5,5 -((1 H -pyrazole-3,5-di- carbonyl)bis(azanediyl))diisophthalic acid, DMA= N , N -dimethylacetamide) was synthesized and characterized by infrared radiation (IR), thermogravimetric analyses (TGA), powder X-ray diffraction spectra (PXRD) and X-ray diffraction. Complex 1 has a three dimensional (3D) framework, which can be simplified as 5,5,5,5-c net with the Schlafi symbol of {43.64.83} {44.65.8}{45.65}2. This luminescent metal-organic framework (MOF) shows selectively sensitive to nitrobenzene and series of nitroaromatic explosives such as 4-nitrotoluene, 1,4-dinitrobenzene, 1,3-dinitrobenzene and 2,4-dinitrotoluene, and exhibits well recyclability. So complex 1 could be used to detect nitroaromatic explosives as a selective sensing material.

Syntheses, structures and photoluminescent properties of Zn(Ⅱ)/Co(Ⅱ) coordination polymers based on flexible tetracarboxylate ligand of 5,5′-(butane-1,4-diyl)-bis(oxy)-di isophthalic acid

Three new mixed-ligand metal-organic frameworks based on 5,5′-(butane-1,4- diyl)-bis(oxy)-diisophthalic acid and transitional metal cations with the help of two ancillary bridging N-donor pyridyl and imidazole linkers, [Zn(L)0.5(4,4′-bpy)]·2(H2O) (1), [M(L)0.5(bib)]·4(H2O) (M = Zn (2), Co (3)), (4,4′-bpy=4,4′–bipyridine, bib=1,4-bis (1H-imidazol-1-yl)-butane), have been synthesized under solvothermal conditions. Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses and thermogravimetric analyses (TGA). Compounds 1–3 display a 3D 3-fold interpenetrated frameworks linked by the L4− ligands, ancillary N-donor linkers and the free water molecules in the crystal lattice. Topological analysis reveals that 1–3 are a (4,4)-connected bbf topology net with the (64·82)(66) topology. The effects of the L4− anions, the N-donor ligands, and the metal ions on the structures of the coordination polymers have been discussed. Furthermore, luminescence properties and thermogravimetric properties of these compounds were investigated.

A Microporous Metal-Organic Framework with Lewis Basic Nitrogen Sites for High C2H2 Storage and Significantly Enhanced C2H2/CO2 Separation at Ambient Conditions.

A novel metal-organic framework (MOF), [Cu2L(H2O)2]·7DMF·4H2O [ZJU-40; H4L = 5,5'-(pyrazine-2,5-diyl)diisophthalic acid], with Lewis basic nitrogen sites has been constructed and structurally characterized. Owing to the combined features of high porosity, moderate pore sizes, and immobilized Lewis basic nitrogen sites, the activated ZJU-40a exhibits the second-highest gravimetric C2H2 uptake of 216 cm(3) g(-1) (at 298 K and 1 bar) among all of the reported MOFs so far. This value is not only much higher than that of the isoreticular NOTT-101a (184 cm(3) g(-1)), but also superior to those of two very promising MOFs, known as HKUST-1 (201 cm(3) g(-1)) and Co-MOF-74 (197 cm(3) g(-1)). Interestingly, the immobilized nitrogen sites in ZJU-40a have nearly no effect on the CO2 uptake, so ZJU-40a adsorbs a similar amount of CO2 (87 cm(3) g(-1)) compared with NOTT-101a (84 cm(3) g(-1)) at 298 K and 1 bar. As a result, ZJU-40a shows significantly enhanced adsorption selectivity for C2H2/CO2 separation (17-11.5) at ambient temperature compared to that of NOTT-101a (8-9), leading to a superior MOF material for highly selective C2H2/CO2 separation.

Synthesis, crystal structure, and luminescent property of a discrete Zn3L3 metallomacrocycle constructed from 5-hydroxyisophthalic acid

An interesting discrete metallomacrocycle (MMC), [Zn3(L)3(H2O)6] · H2O (I), has been prepared by means of self-assembly of Zn(II) salt, 5-hydroxyisophthalic acid (H2L) as organic linker and 5,5’-(pyridine-2,6-diyl)diisophthalic acid (H4L’) as structure-directing agentunder hydrothermal condition. In complex I, the planar trinuclearmetal-organic macrocycles are arranged into 2D sheet layers connected by strong hydrogen bonded between OH groups of the ligands. Then they stack into 3D supramolecular architecture in–ABAB–array way to give a small 1D open channel along the c axis (CIF file CCDC no. 1053024). Additionally, thermal stability and luminescence properties of I were also investigated.

Solvent-regulated assemblies of four Zn(II) coordination polymers constructed by flexible tetracarboxylates and pyridyl ligands

Four unique complexes with diverse coordination architectures were synthesized upon complexation of 5,5-(1,4-phenylenebis (methylene))bis (oxy)- diisophthalic acid (H4L) with zinc ions by using different solvent. namely, {[Zn(H2L) (bpp)]·DEF}n (1), {[Zn2(L) (bpp)2]·4H2O}n (2), {[Zn2(L) (pdp)2]·3H2O·DEF}n (3), {[Zn2(L) (pdp)2].4H2O}n (4). Complexes 1,2 and 3,4 are obtained by varying solvents to control their structures. The size of solvent molecular plays an important role to control different structure of these compounds. Compound 1 is 2D waved framework with (4, 4) grid layer as sql topology. Compound 3 displays a (4,6)-connected 2-nodal net with a fsc topology. Compounds 2 and 4 are all three-dimensional network simplified as (4,4)-connected 2-nodal net with a bbf topology. The photochemical properties of compounds 1–4 were tested in the solid state at room temperature, owing to their strong luminescent emissions, complexes 1–4 are good candidates for photoactive materials.

Water-Stable Anionic Metal-Organic Framework for Highly Selective Separation of Methane from Natural Gas and Pyrolysis Gas.

A 3D water-stable anionic metal-organic framework [Zn4(hpdia)2]·[NH2(CH3)2]·3DMF·4H2O (FJI-C4) was constructed based on an elaborate phosphorus-containing ligand 5,5'-(hydroxyphosphoryl)diisophthalic acid (H5hpdia). FJI-C4 with narrow one-dimensional (1D) pore channels exhibits high selectivity of C3H8/CH4 and C2H2/CH4. It is the first time for the MOF which contains phosphorus for selective separation of methane from natural gas and pyrolysis gas.

The Utilization of Amide Groups To Expand and Functionalize Metal-Organic Frameworks Simultaneously.

A new stepwise ligand-elongation strategy by amide spacers is utilized to prepare isoreticularly high-porous metal-organic frameworks (MOFs), namely, quasi-mesoporous [Cu2 (PDBAD)(H2 O)]n (H4 PDBAD=5,5'-((4,4'-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis(benzoyl))bis(azanediyl))diisophthalic acid; NJU-Bai22: NJU-Bai for Nanjing University Bai's group), and mesoporous [Cu2 (PABAD)(H2 O)]n (H4 PABAD=5,5'-((4,4'-((4,4'-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis(benzoyl))bis (azanediyl))bis(benzoyl))bis(azanediyl))diisophthalic acid; NJU-Bai23). Compared with the prototypical MOF of [Cu2 (PDAD)(H2 O)]n (H4 PDAD=5,5'-(pyridine-3,5-dicarbonyl)bis(azanediyl)diisophthalic acid; NJU-Bai21, also termed as PCN-124), both MOFs exhibit almost the same CO2 adsorption enthalpy and CO2 selectivity values, and better capacity for CO2 storage under high pressure; these results make them promising candidate materials for CO2 capture and sequestration. Interestingly, this new method, in comparison with traditional strategies of using phenyl or triple-bond spacers, is easier and cheaper, resulting in a better ability to retain high CO2 affinity and selectivity in MOFs with large pores and high CO2 storage capacity. Additionally, it may lead to the high thermal stability of the MOFs and also their tolerance to water, which is related to the balance between the density of functional groups and pore sizes. Therefore, this strategy could provide new opportunities to explore more functionalized mesoporous MOFs with high performance.

A Robust Luminescent Tb(III)-MOF with Lewis Basic Pyridyl Sites for the Highly Sensitive Detection of Metal Ions and Small Molecules.

A new luminescent terbium-metal-organic framework [Tb3(L)2(HCOO)(H2O)5]·DMF·4H2O (1) (H4L = 4,4'-(pyridine-3,5-diyl)diisophthalic acid) has been successfully assembled by Tb(3+) ions and an undeveloped pyridyl-tetracarboxylate. Compound 1 exhibits a 3D porous (3,8)-connected (4.5(2))2(4(2).5(12).6(6).7(5).8(3)) topological framework with fascinating 1D open hydrophilic channels decorated by uncoordinated Lewis basic pyridyl nitrogen atoms. In particular, the Tb-MOF (1) can detect Cu(2+) ions with high selectivity and sensitivity, and its luminescence is nearly entirely quenched in N,N-dimethylformamide (DMF) solution and biological system. In addition, 1 still has high detection for the trace content of nitromethane with 70 ppm, which suggests that 1 is a promising example of dual functional materials with sensing copper ions and nitromethane.

A New Generation Co‐Assembled Small Molecular Gel with Polyaniline: Exciting Mechanical, Electronic and Photovoltaic Properties

SummaryFolic acid (F), Fmoc‐protected phenylalanine (FP) and 5,5′‐(1,3,5,7‐tetraoxopyrrolo[3,4‐f]isoindole‐2,6‐diyl) diisophthalic acid (PMDIG) are used to produce co‐assembled gels with polyaniline(PANI). The formation of PANI inside the gel matrices are confirmed by FTIR and UV‐vis spectroscopy. UV‐vis spectra also exhibit the polaron band transitions of the doped PANI. Both F‐PANI and PMDIG‐PANI gels exhibit fibrillar network morphogy but the branching is more in the F‐PANI gel. The FP‐PANI gel however exhibits nanotubular morphology. The dc conductivity values of F‐PANI, FP‐PANI and PMDIG‐PANI xerogels are 0.14 × 10−4, 0.12 × 10−1 and 0.3 × 10−4 S/cm, respectively. The current–voltage (I–V) curves of the F‐PANI gel shows a negative differential resistance(NDR) property both at forward and backward bias. The I–V property of the FP‐PANI xerogel resembles to the behavior of a semiconductor‐metal junction and that of PMDIG‐PANI xerogel exhibits a signature of rectification property. A dye‐sensitized solar cell is also fabricated using the PMDIG‐PANI gel with a power conversion efficiency of 0.1%.

Central-metal exchange, improved catalytic activity, photoluminescence properties of a new family of d(10) coordination polymers based on the 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid ligand.

The rigid and planar tetracarboxylic acid 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid (H4L), incorporating a triazole group, has been used with no or different pyridine-based linkers to construct a family of d(10) coordination polymers, namely, {[H2N(CH3)2]3[Cd3(L)2(HCOO)]}n (), {[Cd2(L)(py)6]·H2O}n (), {[H2N(CH3)2] [Cd2(L)(HCOO)(H2O)4]}n (), {[Zn(H2L)]·H2O}n (), and {[Zn(H2L)(4,4'-bipy)0.5]·C2H5OH·H2O}n () (py = pyridine, 4,4'-bipy = 4,4'-bipyridine). constructs a 3D porous network containing two kinds of channels: one is filled with coordinated HCOO(-) anions, and the other with [H2N(CH3)2](+) cations. The framework of can be described as a rare (5,6,7)-connected net with the Schläfli symbol of (4(12)·5·6(2))(4(5)·5(3)·6(2))2(4(8)·5(3)·6(8)·8(2))2. The Cd(ii) ions in are connected through the carboxylate ligands to form a 2D layer, with aperture dimensions of ∼15.1 Å × 16.2 Å. The network of features a 3D (3,4)-connected (6·8·10)2(6·8(3)·10(2)) topology. A 3D network with the (4(2)·6·8(3)) topology of possesses an open 1D channel with the free volume of 29.2%. is a 2D layer structure with the (4(2)·6(3)·8)(4(2)·6) topology. The fluorescence lifetime τ values of are on the nanosecond timescale at room temperature. In particular, central-metal exchange in leads to a series of isostructural M(ii)-Cd frameworks [M = Cu (), Co (), Ni ()] showing improved catalytic activity for the synthesis of 1,4,5,6-tetrahydropyrimidine derivatives. Based on this, a plausible mechanism for the catalytic reaction has been proposed and the reactivity-structure relationship has been further clarified.