Dicarboxylate Ligands Research Articles

Syntheses, Structures, and Photocatalytic and Sonocatalytic Degradations of Methyl Blue of Cu(II) and Mn(II) Coordination Polymers Based on Tri(triazole) and Dicarboxylate Ligands

Cu(II) and Mn(II) coordination polymers [Cu(ttpa)(sub)]n (Cuttpa or 1) and {[Mn2(ttpa)2(nip)2(H2O)2]·3H2O}n (Mnttpa or 2) (ttpa = tris(4-(1,2,4-triazol-1-yl)phenyl)amine, H2sub = suberic acid, nip = 5-nitroisophthalicate) were hydrothermally prepared and the structures were characterized. Cuttpa exhibited a 2D (4,4) network based on [Cu2(COO)4] dimers with upper and lower dangled ttpa ligands and a 2D → 3D polythreaded network. Mnttpa showed a 2D (4,4) network with dangled uncoordinated triazole rings from ttpa ligands and nitro groups from nip2− ligands and a 2D → 3D polythreaded network. Eg data of Cuttpa and Mnttpa were 1.88 eV and 2.11 eV. Cuttpa and Mnttpa exhibited good catalytic activity for the decomposition of methyl blue (MB) under visible light and supersound irradiation. The decomposition mechanism using Cuttpa was explored. The holes (h+) and •OH hydroxyl radicals played the main roles, and the •O2− superoxide radicals played certain auxiliary roles in the decomposition of MB within the Cuttpa catalyst.

Polypod Carboxylic Acid-Rare Earth Complex with High Cyclic Stability for Nitrobenzene Compound Detection.

The 5',5''-bis(4-carboxyphenyl)-[1,1':3',1'':3'',1'''-quaterphenyl]-4,4'''-dicarboxylic (H4L1) ligand has a large conjugated rigid planar structure and good absorption of ultraviolet radiation, which can provide effective "antenna effect". However, rare earth complexes using H4L1 as the sole ligand have not been reported. In this paper, rare earth Eu was combined with H4L1 ligand to produce organic rare earth composite L1-Eu by solvothermal synthesis method. It was found through fluorescence spectroscopy that the emission of L1-Eu complex has a linear response to nitrobenzene compounds. The L1-Eu composite material has a low detection limit for nitrobenzene compounds, with detection limits of 0.910, 8.401, 24.510, and 8.171 µM for nitrobenzene, o-nitrophenol, m-nitrophenol, and p-nitrophenol, respectively. Further more the L1-Eu complex can sensitively respond to nitrobenzene compounds while resisting interference from common metal ions and organic solvents. In particular, L1-Eu composite material has good stability and recyclability. Therefore, L1-Eu composite material can serve as a fluorescent probe for specific detection of nitrobenzene compounds. We believe that the L1-Eu complex provides a new method for fluorescence detection of nitrobenzene compounds.

Regulation on the ligand fluorescence in UiO-66-Y metal-organic frameworks for effective detection of nitro-aromatic explosives

Rapid, sensitive and highly selective detection of nitro-aromatic explosives (NAEs) has become one of the most pressing environmental and safety issues. Metal-organic frameworks (MOFs) offer new possibilities for the development of new photoactive materials with excellent sensing properties. In this paper, three robust UiO-66-type fluorescent MOFs were prepared from the self-assembly of yttrium cations (Y3+) and linear dicarboxylic acid ligands, named terephthalic acid (BDC), 2-hydroxyterephthalic acid (OHBDC) and 2,5-dihydroxyterephthalic acid (DHBDC). The solid and solution fluorescence properties of three MOFs were successfully modulated by regulating the number of –OH functional groups from zero to two. At 370 nm excitation, Y-BDC MOF without –OH group was almost non-fluorescent, Y-OHBDC MOF with one –OH group emitted blue fluorescence, and Y-DHBDC MOF with two –OH groups emitted green fluorescence. Thanks to the suitable porous structures and stable frameworks, Y-OHBDC and Y-DHBDC MOFs both can quantificationally detect at least seven nitro-aromatic explosives (NAEs) by a fluorescence quenching process. Remarkably, the detection performance for 2,4,6-trinitrophenol (TNP) is the most outstanding with the KSV values of 8.4 × 104 M−1 and 2.1 × 105 M−1. Fast response, high sensitivity, strong anti-interference ability and good reusability make UiO-66-Y MOFs potential fluorescent sensors for TNP.

Selective Adsorption of Dyes and Fe3+ Sensing via Tb3+ Incorporation in an Anionic Cadmium-Organic Framework.

A three-dimensional (3D) anionic cadmium-organic framework, namely [(CH3)2NH2][Cd1.5(DMTDC)2] ⋅ 2DMA ⋅ 0.5H2O (Cd-MOF; DMA=N,N-dimethylacetamide), was successfully synthesized under solvothermal conditions by using a linear thienothiophene-containing dicarboxylate ligand, 3,4-dimethylthieno [2,3-b]-thiophene-2,5-dicar-boxylic acid (H2DMTDC). Single-crystal X-ray diffraction analysis reveals that Cd-MOF exhibits a 3D anionic framework with pcu α-Po topology, featuring rectangle and rhombus-shaped channels along b- and c- axis direction. Cd-MOF demonstrates selective adsorption of cationic dyes over anionic and neutral dyes. Additionally, Tb3+-loaded Cd-MOF serves as a fast-response fluorescence sensor for the sensitive detection of Fe3+ ions with a low limit of detection (8.90×10-7 M) through fluorescence quenching.

Polyoxometalate-Dicarboxylate Hybrid Dimers with {SiW10Cr2} Nodes: Syntheses, Structures, and Mass Spectrometric Characterization.

The current study describes a new family of hybrid dimers constructed from secondary building blocks based on a dichromium-substituted silicodecatungstate, {SiW10Cr2}, and flexible dicarboxylate ligands of varied lengths. All five polyoxometalate-organic hybrid compounds exhibit an entropically favored, cyclic dimer motif that contains just two {SiW10Cr2} clusters─the minimum to form a closed loop, linked by two aliphatic dicarboxylates, as revealed by single-crystal X-ray diffraction. Due to the kinetic inertness of such Cr3+-based hybrid dimers, ESI-MS has become a particularly useful technique for the characterization of these paramagnetic, NMR-unfriendly systems.

Effect of Anchoring Dynamics on Proton-Coupled Electron Transfer in the Ru(bda) Coordination Oligomer on a Graphitic Surface.

The oligomeric ruthenium-based water oxidation catalyst, Ru(bda), is known to be experimentally anchored on graphitic surfaces through CH-π stacking interactions between the auxiliary bda ([2,2'-bipyridine]-6,6'-dicarboxylate) ligand bonded to ruthenium and the hexagonal rings of the surface. This anchoring provides control over their molecular coverage and enables efficient catalysis of water oxidation to dioxygen. The oligomeric nature of the molecule offers multiple anchoring sites at the surface, greatly enhancing the overall stability of the hybrid catalyst-graphitic surface anode through dynamic bonding. However, the impact of this dynamic anchoring on the overall catalytic mechanism is still a topic of debate. In this study, a crucial proton-coupled electron transfer event in the catalytic cycle is investigated using DFT-based molecular dynamics simulations plus metadynamics. The CH-π stacking anchoring plays a critical role not only in stabilizing this hybrid system but also in facilitating the proton-coupled electron transfer event with possible vibronic couplings between the anchoring bonds motion and charge fluctuations at the catalyst - graphitic surface interface. Furthermore, this computational investigation displays the presence of a quartet spin state intermediate that can lead to the experimentally observed and thermodynamically more stable doublet spin state.

Fine-tuning porosity of In-MOFs with ncb topology based on reticular chemistry for one-step purification C2H4 from ternary C2H6/C2H4/C2H2 mixtures

One-step purification of C2H4 from ternary C2H6/C2H4/C2H2 mixtures by single adsorbent is of great industrial significance, but few adsorbents can achieve this purpose. Herein, four isoreticular In-MOFs, In-BDC-AINA, In-ATC-INA, In-Fum-INA, and In-Fum-AINA (H2BDC, H2ATC, H2Fum, HINA, and HAINA are 1,4-benzenedicarboxylic acid, 2-amino-terephthalic acid, fumaric acid, isonicotinic acid and 3-amino-isonicotinic acid, respectively), were designed and synthesized by the guidance of reticular chemistry, using the known In-BDC-INA as the platform, through amino modification and ligand shortening approaches. In-ATC-INA and In-BDC-AINA were aminations of H2BDC and HINA, respectively. In-Fum-INA is replacing H2BDC to shorter H2Fum. In-Fum-AINA is obtained by further amination of In-Fum-INA. Due to the molar ratio of isoniacic and dicarboxylic ligands in this series structure is 2/1, they exhibit different site numbers, site distributions, pore sizes and pore volumes after regulation. These frameworks without open metal sites provided the ability of C2H6/C2H4 inversion adsorption. The amino modification and ligand shortening approaches successfully improved the selectivity of C2H2/C2H4, and the equimolar C2H2/C2H4 selectivities of In-ATC-INA (1.82) and In-Fum-INA (2.81) were higher than that of In-BDC-INA (1.73) calculated by IAST method. The breakthrough results show that In-BDC-INA, In-ATC-INA and In-Fum-INA can achieve one-step separation of the ternary C2 mixtures and the C2H4 yields are 0.08, 0.13 and 0.09 mmol/g, respectively, demonstrating that the two approaches have successfully improved the gas separation performance. In addition, these materials possess exceptional thermal and chemical stability, the low-cost ligand used in In-Fum-INA synthesis further enhances its potential application for industrial gas separation.

Modulated Self-Assembly of Catalytically Active Metal-Organic Nanosheets Containing Zr6 Clusters and Dicarboxylate Ligands.

Two-dimensional metal-organic nanosheets (MONs) have emerged as attractive alternatives to their three-dimensional metal-organic framework (MOF) counterparts for heterogeneous catalysis due to their greater external surface areas and higher accessibility of catalytically active sites. Zr MONs are particularly prized because of their chemical stability and high Lewis and Brønsted acidities of the Zr clusters. Herein, we show that careful control over modulated self-assembly and exfoliation conditions allows the isolation of the first example of a two-dimensional nanosheet wherein Zr6 clusters are linked by dicarboxylate ligands. The hxl topology MOF, termed GUF-14 (GUF = Glasgow University Framework), can be exfoliated into monolayer thickness hns topology MONs, and acid-induced removal of capping modulator units yields MONs with enhanced catalytic activity toward the formation of imines and the hydrolysis of an organophosphate nerve agent mimic. The discovery of GUF-14 serves as a valuable example of the undiscovered MOF/MON structural diversity extant in established metal-ligand systems that can be accessed by harnessing the power of modulated self-assembly protocols.

Redox-Active Ruthenium-Organic Polyhedra with Tunable Surface Functionality and Porosities.

Dinuclear ruthenium paddlewheel complexes exhibit high structural stability in redox reactions. The use of these chemical motifs for the construction of Ru-based metal-organic polyhedra (RuMOPs) provides a route for redox-active porous materials. However, there are few studies on the synthesis and characterization of RuMOPs due to the difficulty in controlling the assembly process via the ligand-exchange reaction of equatorial acetates of the diruthenium tetraacetate precursors with dicarboxylic acid ligands. In this study, we synthesized three novel cuboctahedral RuMOPs based on the Ru2(II/III)-paddlewheel units with different alkyl functionalizations on the benzene-1,3-dicarboxylate moieties. We evaluated the effect of external functionalization on the molecular packing and the porous and redox properties. The electrochemical measurements revealed the multielectron transferred redox process where the electron-donating/-withdrawing nature of the functional groups allows the control of the redox behavior.

Four Lanthanide(III) Metal-Organic Frameworks Fabricated by Bithiophene Dicarboxylate for High Inherent Proton Conduction.

Currently, it is still a challenge to directly achieve highly stable metal-organic frameworks (MOFs) with superior proton conductivity solely through the exquisite design of ligands and the attentive selection of metal nodes. Inspired by this, we are intrigued by a multifunctional dicarboxylate ligand including dithiophene groups, 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), and lanthanide ions with distinct coordination topologies. Successfully, four isostructural three-dimensional lanthanide(III)-based MOFs, [Ln2(DTD)3(DEF)4]·DEF·6H2O [LnIII = TbIII (Tb-MOF), EuIII (Eu-MOF), SmIII (Sm-MOF), and DyIII (Dy-MOF)], were solvothermally prepared, in which the effective proton transport will be provided by the coordinated or free solvent molecules, the crystalline water molecules, and the framework components, as well as a large number of highly electronegative S and O atoms. As expected, the four Ln-MOFs demonstrated the highest proton conductivities (σ) being 0.54 × 10-3, 3.75 × 10-3, 1.28 × 10-3, and 1.92 × 10-3 S·cm-1 for the four MOFs, respectively, at 100 °C/98% relative humidity (RH). Excitingly, Dy-MOF demonstrated an extraordinary ultrahigh σ of 1 × 10-3 S·cm-1 at 30 °C/98% RH. Additionally, the plausible proton transport mechanisms were emphasized.

Electrochemical ammonia oxidation catalyzed by ruthenium complexes: investigation of substituent effect of axial pyridine ligands

Abstract We have examined catalytic ammonia oxidation using ruthenium complexes bearing 2,2′-bipyridine-6,6′-dicarboxylate ligand and axial 3- and 4-substituted pyridine ligands under electrochemical conditions to study the substituent effect of the axial pyridine ligands. Ruthenium complex bearing 3,4-dibromopyridine ligands shows the highest catalytic activity to produce up to 145 equivalents of dinitrogen based on the catalyst.

3D WO3/BiMOF/Bi2WO6 with rich vacancies defects self-assembled via H2BDC anchoring Bi source of Bi2WO6 for high-performance visible light-driven nitrogen fixation and organic pollutant degradation

A novel photocatalyst WO3/BiMOF/Bi2WO6 was prepared by self-assembly of benzene dicarboxylic acid ligand (H2BDC) anchoring Bi source on the surface of Bi2WO6 to form BiMOF, in which WO3 spherical particles were scattered uniformly. Thereby, an amount of metal and oxygen vacancies (VM + O) are generated. The 3D flower-like spherical photocatalyst has a large specific surface area and close interfacial contacts, which can provide sufficient channels for carrier migration. The introduction of BiMOF enhanced the light absorption capability of photocatalyst. As a result, the flower-like WO3/BiMOF/Bi2WO6 structure exhibits excellent nitrogen fixation as well as high-level photocatalytic activity in degrading Rhodamine B (RhB) and tetracycline (TC) under visible light. For one thing, WO3/BiMOF/Bi2WO6 produce ammonia up to 227 μmol L−1 h−1. For another, the degradation efficacy displayed by RhB 99.3% in 15 min and TC 93.6% degradation in 50 min, respectively. In addition, the catalysts showed excellent cyclic stability, with constant degradation efficiencies for at least 4 cycles. The experimental results of free radical scavenging showed that holes (h+) and superoxide radical (·O2−) were the main active substances in the photodegradation process. Therefore, the photocatalytic mechanism of 3D flower-like WO3/BiMOF/Bi2WO6 was also proposed.

Adsorptive separation of Xe/Kr mixtures by microporous lanthanide metal-organic frameworks with high thermal stability

Efficient separation of Xenon (Xe) and Krypton (Kr) is a significant process for their wide industrial applications and potential environmental concerns. Owing to the inert atomic gases (Xe and Kr) nature with similar physical and chemical properties, it is a great challenge to achieve efficient separation of the Xe/Kr mixture. Herein, we report a series of microporous lanthanide based metal-organic frameworks Ln (BTC) (H2O)·(DMF)1.1 (Ln-MOF) (Dy-BTC (1), Er-BTC (2), and Yb-BTC (3)) with ultrahigh thermal stability for adsorptive Xe/Kr separation. These three isostructural Ln-MOFs consisted of lanthanide metal ions and 1,3,5-benzene dicarboxylate ligands that possess a square channel with pore sizes of 6–7 Å. By substitution of Ln ions, Yb-BTC shows the smallest pore size among the three compounds which enables its obvious higher Xe/Kr selectivity compared with the other two Ln-MOFs. Yb-BTC exhibits a moderately high Xe uptake of 2.5 mmol/g (298 K and 1 bar), and a significantly high Xe/Kr uptake ratio of 3.8, indicative of its great potential for separation of Xe/Kr mixture. The effective Xe/Kr separation ability of Yb-BTC was also confirmed by a breakthrough experiment.

1,1ʹ-Dimethyl-4,4ʹ-bipyridinium as a multivalent structure-directing counterion to anionic uranyl ion polycarboxylate complexes

Seven uranyl ion complexes with polycarboxylates have been synthesized under solvo-hydrothermal conditions and in the presence of 1,1ʹ-dimethyl-4,4ʹ-bipyridinium (Me2bipy2+) as structure-directing counterion. Two complexes were obtained with phthalate (pht2–), [Me2bipy]2[(UO2)4(pht)4(O)2] (1), which is a discrete, bis(μ3-oxo-bridged) tetranuclear species, and {[Me2bipy][(UO2)3(pht)4(H2O)]}n (2), which crystallizes as a monoperiodic coordination polymer. The complex obtained with citric acid (H4cit), {[Me2bipy][UO2(Hcit)]2·H2O}n (3), assumes a well-known monoperiodic form. {[Me2bipy][(UO2)2(Hthftc)2]}n (4), obtained from tetrahydrofurantetracarboxylic acid (H4thftc), is also a monoperiodic polymer further assembled into layers through hydrogen bonding, the packing defining channels containing columns of stacked counterions. The previously reported {[Me2bipy][(UO2)2(tdc)3]}n (5), where tdc2– is 2,5-thiophenedicarboxylate, is a diperiodic hcb network, with the counterions crossing the hexanuclear rings. One experiment with pimelate (pim2–) gave the two complexes {[Me2bipy][(UO2)2(pim)3]}n (6) and {[Me2bipy][(UO2)4(pim)5(DMA)2]}n (7) (DMA = N,N-dimethylacetamide). Both 6 and 7 are diperiodic assemblies, but while 6 has the KIa topology previously found in other uranyl ion complexes with elongated dicarboxylate ligands, 7 is a very intricate and thick assembly with a packing displaying interdigitation. The weak interactions formed by the counterions are discussed through examination of Hirshfeld surfaces.

Structure elucidation and topological studies of new lanthanide-organic frameworks (UPMOFs) synthesised via solvothermal route using mixed dicarboxylate linkers of 1,4-benzenedicarboxylic acid and 4,4-oxybis benzoic acid

The new lanthanide-organic frameworks (UPMOFs) were solvothermally synthesised using M(NO3)3·6H2O (M = La, Ce, Pr and Nd) metal salts with mixed dicarboxylate ligands namely, 1,4-benzenedicarboxylic acid (H2BDC) and 4,4-oxybis benzoic acid (H2OBA). The successful synthesis produced a series of four three-dimensional (3D) UPMOFs identified as [La(BDC)(OBA)(H2O)2].H2O (UPMOF710 (1)), [Ce(BDC)(OBA)(H2O)2].H2O (UPMOF711 (2)), [Pr(BDC)(OBA)(H2O)2].H2O (UPMOF712 (3)) and [Nd(BDC)(OBA)(H2O)2].H2O (UPMOF713 (4)). Comprehensive characterisations were performed on the newly synthesised UPMOFs, encompassing techniques such as infrared spectra (IR), powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), Brunauer-Emmet-Teller (BET) and the structural elucidation was conducted using single-crystal X-ray diffraction (SCXRD). Notably, all four 3D UPMOFs were crystallised in a monoclinic sytem with different space groups. The UPMOFs (1) had a P21/n space group while the 2–4 were crystallised in the space group of I2/a. Consequently, the 2–4 UPMOFs are classified as isostructural MOFs. Remarkably, the topological analysis unveiled a novel topology denoted as upm, which has not been observed in the realm of reticular chemistry.

A novel 2D Eu-MOF as a dual-functional fluorescence sensor for detection of benzaldehyde and Fe3.

Lanthanide metal-organic frameworks (Ln-MOFs) have unique advantages in sensing due to their excellent optical properties. In this study, we synthesized a dicarboxylic acid ligand with amide groups and successfully synthesized a novel two-dimensional (2D) MOF with the molecular formula C42H31EuN4O10 (Eu-MOF) by a solvothermal method. Single-crystal X-ray diffraction showed that amide groups are exposed on the outside of the two-dimensional coordination layer, with the possibility of recognizing specific molecules through hydrogen bonding interactions. The ligand's "antenna effect" enables Eu-MOF to emit a strong luminescence characterized by the "f-f" transition. Further studies have revealed that Eu-MOF could be used as a bifunctional fluorescent probe for the selective detection of benzaldehyde and Fe3+. The sensing mechanism has been analyzed in detail through powder X-ray diffraction (PXRD) analysis, UV-vis spectroscopy, fluorescence lifetime measurement, and density functional (DFT) theory calculation. This design and research can provide a reference for subsequent related work.

2,2′-Bipyridine-4,4′-dicarboxylic acid ligand engineered CsPbBr3 perovskite nanocrystals for enhanced photoluminescence quantum yield with stable display applications

2,2′-Bipyridine-4,4′-dicarboxylic acid ligand modified lead halide perovskite nanocrystals show enhanced optical properties with increased stability.

Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu3+ and Tb3+ metal–organic frameworks: a combined experimental and computational study

Replacement of a phenyl moiety with a 3D-carborane cluster induces a more effective energy transfer on lanthanide ions.

Porphyrin-Based Two-Dimensional Metal-Organic framework nanosheets for efficient photocatalytic CO2 transformation

2D metal − organic framework (MOF) nanosheets have been demonstrated to exhibit excellent properties and prospects in various aspects, especially in photocatalysis. However, the design and direct preparation of 2D MOF photocatalyst is highly desirable but still challenging. Herein, a novel 2D porphyrin-based MOF Fe-DBP(Co), which is assembled by dicarboxylic porphyrin ligands and the unprecedented undecametallic ferric-oxo clusters, is designed and developed. The unique nanosheet morphology and assembled layered structure endows the photocatalyst with higher electron-hole separation efficiency and longer photogenerated carrier lifetime compared to the analogous MOFs. Consequently, Fe-DBP(Co) exhibits strikingly excellent and stable photocatalytic performance in CO2 cycloaddition, and the reaction rate of 103.2 mmol∙g−1∙h−1 is among the state-of-the-art cases for MOF-photocatalyzed CO2 cycloaddition. The underlying mechanism investigation suggested that photogenerated electrons transferred from CoDBP ligands to the Fe clusters, and the abundant electrons and holes promoted the generation of Fe(II) and Co(III) respectively, leading to excellent catalytic performance. This work proposes a new strategy to design and develop efficient MOF photocatalysts for photocatalytic transformation of CO2.

A mesoporous ionic metal-organic framework decorated by flexible alkyl imidazolium bromide as heterogeneous catalyst for efficient conversion of CO2 to cyclic carbonates

A mesoporous ionic MOF-based catalyst (Br−)C3H7-Imidazolium-MOF-1 for the cycloaddition of CO2 to epoxides (CCE) was synthesized by template-assisted method, and its composite and structure were determined by FT-IR, PXRD, NMR, SEM, TEM, XPS and N2 adsorption. (Br−)C3H7-Imidazolium-MOF-1, is constructed by Zr6O4(OH)4 clusters and linear dicarboxylic acid ligands covalently modified by flexible alkyl imidazolium groups (1-methylene-3-propyl-imidazolium bromide). By the synergistic effect of Zr4+ Lewis acid sites and Br− nucleophiles, (Br−)C3H7-Imidazolium-MOF-1 shown superior catalytic performance for the cycloaddition of CO2 to epichlorohydrin in the absence of any co-catalyst under mild conditions. Small steric hindrance from the flexible imidazolium groups and rapid mass transport of reactants and products in the mesoporous catalyst acted synergistically to promote this process. A firm bond between the imidazolium bromide and the framework of (Br−)C3H7-Imidazolium-MOF-1 made it a recyclable heterogeneous catalyst. Furthermore, several additional coupling reactions were investigated with other epoxides as substrates.