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[Display omitted] • Amorphous/crystalline thiophene-based MOFs nanobelts were synthesized by etching nickel–iron foam with thiophene acid. • NiFe-TDC 0.05 exhibits the excellent OER performances (η 100 = 256 mV) • The assembled water splitting device only require a voltage of 1.78 V to achieve a current density of 100 mA cm−2. The oxygen evolution reaction (OER) is a complex four-electron transfer process that poses a significant challenge to the efficient production of hydrogen through water splitting. However, developing non-noble metal electrocatalyst with excellent OER performance is still a big challenge. Herein, we propose a new strategy for the in-situ growth of two-dimensional amorphous/crystalline thiophene-based Ni-Fe metal–organic frameworks (MOFs) using Ni-Fe foam (NFF) as metal source and current collector, and thiophene-2,5-dicarboxylic acid (TDC) as corrosion agent and ligand. TDC was ionized at high temperature to produce H+ ions that etch NFF to release Ni2+ and Fe2+ ions, which were coordinated with TDC to in situ synthesize two-dimensional Ni-Fe thiophenedicarboxylate coordination polymer (NiFe-TDC) nanobelts on NFF. The unique structure and synergistic effect of Ni and Fe ions of NiFe-TDC 0.05 result in the excellent OER performance with an overpotential of 224 and 256 mV at current densities of 10 and 100 mA cm−2, respectively, and it can run stably for 100 h at a current density of 100 mA cm−2, indicating the outstanding stability. Furthermore, NiFe-TDC 0.05 remains the excellent OER performance with an extremely low potential of 196 and 271 mV at current densities of 10 and 100 mA cm−2 in seawater with 1 mol L-1 (M) KOH, respectively. The assembled NiFe-TDC 0.05 || Pt/C water electrolysis cell achieves a current density of 100 mA cm−2 at a low voltage of 1.78 V. The work provides a new method to prepare two dimensional MOFs for efficient water oxidation. [ABSTRACT FROM AUTHOR]

Stimuli-responsive coordination polymers (CPs) are among one of the most prolific research areas in developing the next-generation functional materials. Their capability of being accurately excited by particular external changes with pre-determined and observable/characterizable behaviors correspond, are the so called "stimuli" and "responsive". Abundant types of CP compounds, especially metal-organic frameworks (MOFs), are of rocketing interest owing to their compositional diversity, structural tunability, and in essence their highly engineerable functionality. This present review is aimed to sketch several common types of stimulation and the corresponding responses for CPs, accompanied with the broad logic and mechanisms underneath. And further from the aspect of material revolution, some representative progresses together with the latest advances of CPbased materials in various fields are covered in attempt to display a broader picture towards the possible prospects of this topic. [ABSTRACT FROM AUTHOR]

Using the mixed-ligand strategy, three metal–organic frameworks were constructed by virtue of the solvothermal reaction. These compounds exhibit similar two-dimensional layered structures and serve as an efficient and economical porous heterogeneous catalyst for Knoevenagel condensation under mild conditions. The yields of Knoevenagel condensation can be reached between 96% and 99% in the presence of catalysts 1–3. Notably, the catalytic performance of 1 through reusability was explored, and it was observed that 1 could be reused up to six cycles with almost consistent catalytic efficiency. [ABSTRACT FROM AUTHOR]

Highly connected molecular building blocks (MBBs) have been demonstrated to play a crucial role in reticular chemistry, particularly in predicting the topologies of metal–organic frameworks. Metal phosphonate clusters exhibit considerable advantages in constructing high-connectivity MBBs, owing to the multiple coordination modes offered by phosphonic ligands. Herein, four metal (M = CoII, MnII) phosphonocarboxylate frameworks (CoPCF-1,2 and MnPCF-1,2) were successfully prepared under solvothermal conditions by utilizing the phosphonocarboxylic ligand, 4′-phosphonobiphenyl-3,5-dicarboxylic acid (H4pbpdc), and their structural characterization was performed using single-crystal X-ray diffraction (SCXRD). The structures feature a duodenary nuclear M12(µ3-OH)2(CO2)12(PO3)6(DMF)6/(CH3COO)4.5 cluster, bearing resemblance to the well-known Wells–Dawson ion from polyoxometallate chemistry. It is the first time a Wells–Dawson type cage has served as an 18-connected molecular building block, forming two kinds of porous metal phosphonocarboxylate frameworks with novel (3,18)-connected gez and gea topologies. Their permanent porosities were confirmed through N2 adsorption studies. Notably, the MBB Co12 cluster-based CoPCF-1 shows a loss and recovery process of µ3-OH through single-crystal-to-single-crystal (SCSC) transformation. The magnetic properties of the four compounds exhibit antiferromagnetic behavior. [ABSTRACT FROM AUTHOR]

Three congenetic Cd-MOFs with different pores were successfully synthesized via solvent-regulated strategy, and they were used as friction materials to regulate the TENG output, which could drive electrolysis systems to promote the direct bromination of aromatic compounds in high yields with good regioselectivity. [Display omitted] Optimizing friction materials based on molecular diversity in a molecular framework system is an effective method to improve the output performance of triboelectric nanogenerators (TENGs). In this study, three cadmium(II) metal–organic frameworks (Cd-MOFs) with different cavities were synthesized solvothermally by the assembly of cadmium nitrate (Cd(NO 3) 2 ·4H 2 O), 4′,4′''-carbonylbis(([1,1′-biphenyl]-3,5-dicarboxylic acid)) (H 4 CBBD), and trans -1,2-bis(4-pyridyl)ethylene (4,4′-bpe) via a solvent-regulated strategy. The topology and porosity of Cd-MOFs could be controlled effectively by the solvent constituents and were demonstrated to be closely related to their triboelectric behaviors. Theoretical calculations and experimental characterizations revealed that the TENGs fabricated by the Cd-MOF with maximum porosity exhibited the best triboelectric performance owing to the enhanced specific surface area and surface potential. In the applications, the high-output TENGs can be successfully used as an efficient power supply for electrochemical systems, enabling the direct bromination of aromatic compounds in high yields with good regioselectivity. This study provides a simple and feasible method to optimize positive friction materials at the molecular level and develops the practical applications of TENGs in electrochemical systems. [ABSTRACT FROM AUTHOR]

Conjugated coordination polymers (c‐CPs) are unique organic–inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows for the modulation of the electronic structure of c‐CPs while maintaining the structural topology. The redox‐state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5‐tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag4TTHQ and Ag4TTBQ (TTBQ=1,2,4,5‐tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two‐dimensional Ag−S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag4TTHQ and 0.5 eV for Ag4TTBQ) and conductivities (0.4 S/cm for Ag4TTHQ and 10 S/cm for Ag4TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag4TTHQ. Consequently, Ag4TTHQ displays a high Seebeck coefficient of 330 μV/K and a power factor of 10 μW/m ⋅ K2, surpassing Ag4TTBQ and the other reported silver‐based c‐CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm2/V ⋅ s in both Ag4TTHQ and Ag4TTBQ. [ABSTRACT FROM AUTHOR]

Conjugated coordination polymers (c‐CPs) are unique organic–inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows for the modulation of the electronic structure of c‐CPs while maintaining the structural topology. The redox‐state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5‐tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag4TTHQ and Ag4TTBQ (TTBQ=1,2,4,5‐tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two‐dimensional Ag−S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag4TTHQ and 0.5 eV for Ag4TTBQ) and conductivities (0.4 S/cm for Ag4TTHQ and 10 S/cm for Ag4TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag4TTHQ. Consequently, Ag4TTHQ displays a high Seebeck coefficient of 330 μV/K and a power factor of 10 μW/m ⋅ K2, surpassing Ag4TTBQ and the other reported silver‐based c‐CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm2/V ⋅ s in both Ag4TTHQ and Ag4TTBQ. [ABSTRACT FROM AUTHOR]

Two novel CoII metal–organic frameworks {[Co(BIMB)2(H2O)2](SO4)·EG·3 H2O}n (I) and {[Co(TIMB)2](SiF6)}n (II) were hydrothermally synthesized by corresponding metal salt with organic ligands 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (TIMB) or 1,4-bis((1H-imidazol-1-yl)methyl)benzene (BIMB). Crystal structural analysis reveals that they exhibit varied structures. Compound I contains two crystallographically unique CoII centers, each lying on an inversion center and having a slightly distorted octahedral environment. The BIMB ligands link the CoII cations to generate a three-dimensional porous framework with a 4-connected uninodal (65.8) topology. Compound II exhibits a two-dimensional sheeted metal-organic structure running parallel to the (0 0 1) plane, in which TIMB ligands join Co2+ centers having a six-coordinated octahedral structure. In the solid state, adjacent sheets are further bridged by guest SiF6- anions via C–H...F hydrogen-bonding interactions, giving rise to a three-dimensional supramolecular network structure with a 2-nodal (3-c)2(6-c) net. The topological analysis suggests that the point Schläfli symbol of compound II is (43)2(46.66.83). In addition, their thermal stabilities have also been investigated. [ABSTRACT FROM AUTHOR]

Nanostructures of a cobalt(II) metal–organic framework (MOF), denoted as 4,4′,4″-s-triazin-1,3,5-triyltri-p-aminobenzoate (TATAB) [[Co2(TATAB)(OH)(H2O)2].H2O.0.6O]n {1}, were successfully synthesized using two different experimental techniques: solvothermal and sonochemical strategies. Remarkably, both methods yielded an identical crystal structure. Various characterization techniques, including powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR), were employed to analyze all the compounds. Compound contains cobalt ions (Co2+) that were determined to be six-coordinated through the analysis of single-crystal X-ray diffraction (SCXRD). The effect of various factors such as temperature, reaction time, reactant concentration, and ultrasonic energy on the synthesis and final morphology of the compounds obtained by sonochemical method was investigated. Finally, Hirshfeld surface analysis (HAS) of compound was conducted. The molecular descriptors obtained at the BLYP/6–311 + + g (d, p) level of theory framework indicate a unique electronic structure for this complex, characterized by low chemical hardness (η = 1.702 eV), high electrophilicity (ω = 3.637 eV), and a narrow HOMO–LUMO gap (1.55 eV). These descriptors suggest that this complex can be considered a favorable nucleophile in interactions with proteins. [ABSTRACT FROM AUTHOR]

Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3‐TAT)2 (TAT=triazatruxene; R=H, Et, n‐Bu, n‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3‐TAT)2 to Ni3(HIBu3‐TAT)2. Partial exfoliation of Ni3(HIBu3‐TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC. [ABSTRACT FROM AUTHOR]

Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3‐TAT)2 (TAT=triazatruxene; R=H, Et, n‐Bu, n‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3‐TAT)2 to Ni3(HIBu3‐TAT)2. Partial exfoliation of Ni3(HIBu3‐TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC. [ABSTRACT FROM AUTHOR]

Lead halide hybrids have shown great potentials in CO2 photoreduction, but challenging to afford C2+ reduced products, especially using H2O as the reductant. This is largely due to the trade‐off problem between instability of the benchmark 3D structures and low carrier mobility of quasi‐2D analogues. Herein, the lead halide dimensionality of robust coordination polymers (CP) was modulated by organic ligands differing in a single‐atom change (NH vs. CH2), in which the NH groups coordinate with interlamellar [PbI2] clusters to achieve the important 2D→3D transition. This first CP based on 3D cationic lead iodide sublattice possesses both high aqueous stability and a low exciton binding energy of 25 meV that is on the level of ambient thermal energy, achieving artificial photosynthesis of C2H5OH. Photophysical studies combined with theoretical calculations suggest the bridging [PbI2] clusters in the 3D structure not only results in enhanced carrier transport, but also promotes the intrinsic charge polarization to facilitate the C−C coupling. With trace loading of Rh cocatalyst, the apparent quantum efficiency of the 3D CP reaches 1.4 % at 400 nm with a high C2H5OH selectivity of 89.4 % (product basis), which presents one of the best photocatalysts for C2 products to date. [ABSTRACT FROM AUTHOR]

Lead halide hybrids have shown great potentials in CO2 photoreduction, but challenging to afford C2+ reduced products, especially using H2O as the reductant. This is largely due to the trade‐off problem between instability of the benchmark 3D structures and low carrier mobility of quasi‐2D analogues. Herein, the lead halide dimensionality of robust coordination polymers (CP) was modulated by organic ligands differing in a single‐atom change (NH vs. CH2), in which the NH groups coordinate with interlamellar [PbI2] clusters to achieve the important 2D→3D transition. This first CP based on 3D cationic lead iodide sublattice possesses both high aqueous stability and a low exciton binding energy of 25 meV that is on the level of ambient thermal energy, achieving artificial photosynthesis of C2H5OH. Photophysical studies combined with theoretical calculations suggest the bridging [PbI2] clusters in the 3D structure not only results in enhanced carrier transport, but also promotes the intrinsic charge polarization to facilitate the C−C coupling. With trace loading of Rh cocatalyst, the apparent quantum efficiency of the 3D CP reaches 1.4 % at 400 nm with a high C2H5OH selectivity of 89.4 % (product basis), which presents one of the best photocatalysts for C2 products to date. [ABSTRACT FROM AUTHOR]

The construction of multifunctional metal-organic frameworks (MOFs) has attracted considerable attention. Two novel Dy-MOFs namely [Dy2(TPTC-2OMe)1.5(H2O)4·H2O]n (1) and {[Dy2(TPTC-2OMe)(H2TPTC-2OMe) (H2O)2]·2H2O}n (2) were obtained by a solvothermal method using 2′,5′-dimethoxy-[1,1′:4′,1″-terphenyl]- 4,4″-dicarboxylic acid (H4TPTC-2OMe) as the ligand. Structure analysis demonstrates that both MOFs 1 and 2 displayed three-dimensional framework structures, in which MOF 1 was with Dy(III) metal chains as nodes, while MOF 2 was with Dy2 binuclear metal clusters as nodes. Interestingly, MOFs 1 and 2 exhibited high thermal and chemistry stabilities and presented relatively high proton conductivity (σ) values of 1.69 × 10-4 S cm-1 and 3.52 × 10-6 S cm-1 at 50 °C and 98% RH. Although there exist a large number of coordinated or free H2O molecules in both structures, it is easier to form an ordered hydrogen-bonding network between the coordinated H2O molecules in the structure of MOFs, resulting in a more excellent proton conductivity of MOF 1. Moreover, MOF 1 exhibited field-induced single-molecule magnet (SMM) behavior with energy barriers (Ueff) of 37.22 K (τ0 = 9.27 × 10-8 s). Furthermore, MOF 1 exhibits obvious second-order nonlinear optical properties. This research provides guidance for the design of novelty multifunctional MOF materials. [ABSTRACT FROM AUTHOR]

As a hybrid material, metal organic frameworks (MOFs) contain unique characteristics for biomedical applications such as high porosity, large surface area, different crystalline morphologies, and nanoscale dimensions. These frameworks are assembled through the interconnection of organic linkers with metal nodes, while the engineering of an MOF for biomedical applications requires versatile linkers with acceptable symmetry. Porphyrin, as an organic linker with interesting photochemical and photophysical properties, attracted the attention of many for engineering the potent multifunctional porphyrinic metal organic frameworks (PMOFs). In this regard, a large number of approaches were conducted for designing robust practical PMOFs with a wide range of applications. In this review, we introduced another perspective of MOFs and coordination polymers constructed from porphyrinic linkers with a special focus on those synthesized by meso-tetrakis (4-carboxyphenyl) porphyrin (TCPP). In the following, we summarized and discussed the different types of PMOFs and their biomedical applications in terms of diagnostic agent, therapeutic platform, and drug delivery vehicle. [ABSTRACT FROM AUTHOR]

Phosphine‐functionalized metal‐organic frameworks (P‐MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development of heterogeneous catalysts. Yet, compared with the ubiquitous phosphine systems in homogeneous catalysis, heterogenization of phosphines in MOFs is still at its early stage. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the P‐MOFs reported in literature. In particular, various catalytic reactions are discussed in detail in terms of phosphine ligand structure‐function relationship, including the potential obstacles for future development. Finally, we discuss the possible solutions, including new types of reactions and techniques as the perspectives for the development of P‐MOF catalysts, highlighting the opportunities and challenges. [ABSTRACT FROM AUTHOR]

Phosphine‐functionalized metal‐organic frameworks (P‐MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development of heterogeneous catalysts. Yet, compared with the ubiquitous phosphine systems in homogeneous catalysis, heterogenization of phosphines in MOFs is still at its early stage. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the P‐MOFs reported in literature. In particular, various catalytic reactions are discussed in detail in terms of phosphine ligand structure‐function relationship, including the potential obstacles for future development. Finally, we discuss the possible solutions, including new types of reactions and techniques as the perspectives for the development of P‐MOF catalysts, highlighting the opportunities and challenges. [ABSTRACT FROM AUTHOR]

ZPD is a type of metal–organic framework based on zinc ions. Its structure contains 2,5 pyridine dicarboxylic acid as ligand, and it was synthesized by the hydrothermal method. Its metal–organic framework has a high surface area, suitable micropores, and a very regular crystalline structure. In this study, Biginelli reaction and chromene synthesis were realized using Cu@ZPD as a catalyst. The prepared products were obtained with high-to-excellent yield (80–96%). The mentioned catalyst was identified by Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET), thermogravimetric analysis (TGA), X-ray diffraction (XRD), field emission–scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) mapping, transmission electron microscopy (TEM), and inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses. By using ICP-OES, Cu loading was detected at nearly 3 wt%. The prepared catalyst can be reused 6 times without significantly losing its catalytic activity. Also, 1HNMR, 13CNMR, and FT-IR spectroscopy was used to identify the products. [ABSTRACT FROM AUTHOR]

Anthraquinone electrode materials are promising candidates for lithium‐ion batteries (LIBs) due to the abundance of anthraquinone and the high theoretical capacity, and good reversibility of the anthraquinone electrodes. However, the active anthraquinone materials are soluble in organic electrolytes, resulting in a sharp decay of capacity during the charge and discharge processes. Herein, we report on a two‐dimensional calcium anthraquinone 2,3‐dicarboxy metal‐organic framework (2D CaAQDC MOF) fabricated using a simple hydrothermal method. The 2D CaAQDC MOF not only effectively inhibits the dissolution of active electrode substances into the electrolyte, but also promotes the diffusion of lithium ion into the pores of the MOF. When used as a cathode for the LIBs, the resulting CaAQDC electrode delivers a high specific capacity of ~100 mAh g−1 at a current density of 50 mA g−1 after 200 cycles, demonstrating its good cycle stability. Even at a high current density of 200 mA g−1, the CaAQDC electrode exhibits a specific capacity of ~60 mAh g−1. The fabricated 2D coordination polymers effectively restrains the dissolution of anthraquinone into the organic electrolyte and enhances the structural stability, which greatly improves the electrochemical performance of anthraquinone. These research results offer a rational molecular design strategy to address the dissolution of this and other active organic electrode materials. [ABSTRACT FROM AUTHOR]

Luminescent lanthanide molecular compounds have recently attracted attention as potential photosensitizers (PSs) for photodynamic therapy (PDT) against malignant cancer tumours because of their predictable systemic toxicity, temporospatial specificity, and minimal invasiveness. A photosensitizer exhibits no toxicity by itself, but in the presence of light and oxygen molecules, it can generate reactive oxygen species (ROS) to cause damage to proteins, nucleic acids, lipids, membranes, and organelles, which can induce cell apoptosis. This review focuses on the latest developments in luminescent lanthanide-based molecular materials as photosensitizers and their applications in photodynamic therapy. These molecular materials include lanthanide coordination complexes, nanoscale lanthanide coordination polymers, and lanthanide-based nanoscale metal–organic frameworks. In the end, the future challenges in the development of robust luminescent lanthanide molecular materials-based photosensitisers are outlined and emphasized to inspire the design of a new generation of phototheranostic agents. [ABSTRACT FROM AUTHOR]

MOFs (Metal organic frameworks) have diverse structures that present great potential for light capture and light conversion. Therefore, MOFs are widely used in the study of photocatalysis. However, there still are some challenges in photocatalytic organic conversion upon MOFs under mild conditions, such as poor light absorption performance. Here, we successfully synthesized a new Cd‐connected two‐dimensional MOF by a simple hydrothermal method, termed [Cd(PLA)(4,4'‐bipy)0.5 ]⋅(DMF) (Cd‐PLA) (PLA= phenylene‐diacetic acid, 4,4'‐bipy= 4,4'‐bipyridine and DMF= N,N'‐dimethyl formamide). The bpy‐containing Cd‐PLA possesses excellent light harvest ability and suitable photocatalysis energy potential, allowing it to be a remarkable photocatalyst with highly efficiency and selectivity for the photo‐oxidation of benzylamine. This work provides an efficient, economical, and green way for oxidation of amines to produce imines under ultraviolet light irradiation. [ABSTRACT FROM AUTHOR]

A coordination network containing isolated pores without interconnecting channels is prepared from a tetrahedral ligand and copper(I) iodide. Despite the lack of accessibility, CO2 is selectively adsorbed into these pores at 298 K and then retained for more than one week while exposed to the atmosphere. The CO2 adsorption energy and diffusion mechanism throughout the network are simulated using Matlantis, which helps to rationalize the experimental results. CO2 enters the isolated voids through transient channels, termed "magic doors", which can momentarily appear within the structure. Once inside the voids, CO2 remains locked in limiting its escape. This mechanism is facilitated by the flexibility of organic ligands and the pivot motion of cluster units. In situ powder X‐ray diffraction revealed that the crystal structure change is negligible before and after CO2 capture, unlike gate‐opening coordination networks. The uncovered CO2 sorption and retention ability paves the way for the design of sorbents based on isolated voids. [ABSTRACT FROM AUTHOR]

Two‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) are emerging as a unique subclass of layer‐stacked crystalline coordination polymers that simultaneously possess porous and conductive properties, and have broad application potential in energy and electronic devices. However, to make the best use of the intrinsic electronic properties and structural features of 2D c‐MOFs, the controlled synthesis of hierarchically nanostructured 2D c‐MOFs with high crystallinity and customized morphologies is essential, which remains a great challenge. Herein, we present a template strategy to synthesize a library of 2D c‐MOFs with controlled morphologies and dimensions via insulating MOFs‐to‐c‐MOFs transformations. The resultant hierarchically nanostructured 2D c‐MOFs feature intrinsic electrical conductivity and higher surface areas than the reported bulk‐type 2D c‐MOFs, which are beneficial for improved access to active sites and enhanced mass transport. As proof‐of‐concept applications, the hierarchically nanostructured 2D c‐MOFs exhibit a superior performance for electrical properties related applications (hollow Cu‐BHT nanocubes‐based supercapacitor and Cu‐HHB nanoflowers‐based chemiresistive gas sensor), achieving over 225 % and 250 % improvement in specific capacity and response intensity over the corresponding bulk type c‐MOFs, respectively. [ABSTRACT FROM AUTHOR]

Two metal-organic frameworks based on Cd(II) and 2-iodo-(2-I-Bdc) and 2,5-diodo-(2,5-I-Bdc)terephthalate were obtained: {[Cd(2-I-Bdc)(Bbi)]} (I) and {[Cd2(2,5-I-Bdc)2(DMF)2(Bbi)]} (II) (Bbi = 1,1'-(1,4-butanediyl)bis(imidazole)). The structures of both complexes were established by X-ray diffraction (CCDC no. 2258217 (I) and 2257566 (II)). [ABSTRACT FROM AUTHOR]

Two nickel metal-organic frameworks (Ni-MOFs) based on a nitrogen-containing rigid tetracarboxylic acid ligand had been synthesized by the hydrothermal method, namely {[Ni(H4L1)0.5(4,4′-bibp) (H2O)]·1.5H2O}n (1) and {[Ni(H4L1)(H2O)2]·H2O}n (2) (H4L1 = 5,5′-(1H-1,2,4-triazole-3,5-diyl)diisophthalic acid, 4,4′-bibp = 4,4′-di (1H-imidazol-1-yl)-1,1′-biphenyl). Crystal structure analysis revealed that the two complexes exhibited varied structures in the presence or absence of the auxiliary N-donor ligand 4,4′-bibp: the complex 1 was a three-dimensional (3D) metal-organic framework with a (1,2,4,5)-connected {4.64.8}2{42.64}3{6}2 topology. In the complex 2, the carboxylate ligand was used as a junction point to form a 2D layered structure with Ni(II). The results showed that the addition of the 4,4′-bibp has a very important effect on the structure of the complexes. Some conventional characterizations were carried out, such as: Infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric (TGA) analyses. Moreover, the ORCA program was used to perform density functional theory (DFT) calculations to investigate the molecular properties of the two complexes. [ABSTRACT FROM AUTHOR]

In this report, a microporous metal–organic framework of [Ca(TDC)(DMA)]n (1) and a two‐dimensional coordination polymer of [Ca(TDC)(DMF)2]n (2), (TDC2−=Thiophene‐2,5‐dicarboxylate, DMA=N, N'‐dimethylacetamide and DMF=N, N'‐dimethylformamide) based on Ca(II) were designed by the effect of solvent, and X‐ray analysis was performed for the single crystals of 1 and 2. Then, compound 1 was synthesized in three different methods and identified with a set of analyses. Compared to other adsorbents, MOFs are widely used in the field of adsorption and separation of various gases due to a series of distinctive features such as diverse and adjustable structures pores with different dimensions, high porosity and surface area with regular distribution of active sites. Therefore, the ability of 1 to uptake single gases (CH4, CO2, C2H2, H2, and N2) and separation of several binary mixtures of gases (CO2/CH4, CO2/N2, CO2/H2 and CO2/C2H2), were investigated using Grand Canonical Monte Carlo simulations. Volumetric and gravimetric adsorption isotherms in various operating conditions, the isosteric heat of adsorption (qst), the chemical potential for each thermodynamic state, and snapshots during the simulation process were reported in all cases. The results obtained from the adsorption simulation indicate that compound 1 has a high capacity for uptake of H2 (16 mmol g−1) and N2 (12.5 mmol g−1), CO2 (6.6 mmol g−1), C2H2 (5 mmol g−1) and CH4 (1.5 mmol g−1) gases at 1 bar. It also performs well in separating CO2 in binary mixtures, which can be attributed to the presence of open metal sites in nodes of 1 and their electrostatic tendency to interact with CO2 containing the higher quadrupole dipole moment compared to other components of the mixture. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) are formed by the self‐assembly of metal centres/clusters and organic ligands. A diverse range of organic ligands can be employed, including nucleobases, amino acids, peptides, proteins, and saccharides et al. Due to the characteristics of large surface area, high porosity, easy surface functionalization and adjustable internal pore size, et al. MOFs have been used as a significant emerging class of biological imaging agents and have attracted great research interest in optical imaging (OI), photoacoustic imaging (PAI), magnetic resonance imaging (MRI), computer tomography (CT) and positron emission tomography (PET) in recent years. This review provides a comprehensive overview of the diverse range of organic ligands utilized in Metal‐organic frameworks, while also delving into the recent advancements, opportunities, and challenges encountered in the realm of bioimaging in recent years. [ABSTRACT FROM AUTHOR]

• La-MOF ({[La 2 (H 2 DHTPA) 3 (H 2 O) 7 ]·4H 2 O} n) was synthesized by a hydrothermal method. • K-La-MOF was obtained using a KMnO 4 oxidation modification method to modify the La-MOF. • q max of K-La-MOF for PO 4 3−, Cd2+, Pb2+ were 87.56, 37.08, 992.99 mg/g, respectively. • q max of K-La-MOF for Cu2+, As3+, As5+ were 190.51, 42.20, 131.66 mg/g, respectively. Metal–organic framework (MOF) materials are novel adsorption materials for water treatment. In this study, La-MOF ({[La 2 (H 2 DHTPA) 3 (H 2 O) 7 ]·4H 2 O} n , H 4 DHTPA denotes 2,5-dihydroxyterephthalic acid) was synthesized by a hydrothermal method. The material had a strong water stability, but its adsorption performance was weak and its processability was poor. K-La-MOF, with good processability, was obtained using a potassium permanganate oxidation modification method to modify the La-MOF. The results showed that the maximum adsorption capacity (q max) of the La-MOF for PO 4 3− was 72.19 mg/g, and the adsorption was monolayer chemical adsorption. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that P was adsorbed on the surface of the La-MOF material in the form of HPO 4 2−. The adsorption properties of the K-La-MOF were also investigated. The results showed that the maximum adsorption capacities of the K-La-MOF for PO 4 3−, Cd(II), Pb(II), Cu(II), As(III), and As(V) were 87.56, 37.08, 992.99, 190.51, 42.20, and 131.66 mg/g, respectively. The adsorption of PO 4 3−, Cd(II), Cu(II), and As(III) by the K-La-MOF was determined to be monolayer chemisorption by fitting adsorption isotherm and kinetics models. The adsorption process of Pb(II) by the K-La-MOF involved both single-molecular-layer and lateral-multi-molecular-layer chemisorption. In contrast, the adsorption of As(V) by the K-La-MOF occurred through both monolayer chemical adsorption and pore physical adsorption. XRD and XPS analyses showed that P, Cd(II), Pb(II), Cu(II), As(III), and As(V) were adsorbed on the K-La-MOF in the forms of PO 4 3−, CdO, PbO and Pb(OH) 2 , CuO, K 3 AsO 4 , and K 4 As 2 O 7 , respectively. [ABSTRACT FROM AUTHOR]

Reactions of Cd(NO 3) 2 with tri-imidazolyl ligands and 4,4′-biphenyldicarboxylic acid resulted in the formation of 2D-MOF and its selective luminescence sensing were investigated. [Display omitted] • 2D-MOF based on tri-imidazolyl ligands and 4,4′-H 2 bpda were synthesized. • Complex 1 exhibits billayered structure with rectangular channels. • Complex 1 can selectively sense Fe3+ by the luminescence quenching method. A Cd(II) metal–organic framework with 4,4′-biphenyldicarboxylic acid (4,4′-H 2 bpda) and 1,3-bis(1-imidazolyl)-5-[4-(1-imidazolyl)-phenoxymethyl]-benzene (ptim), {[Cd 2 (NO 3) 2 (bpda)(ptim) 2 ]·2DMF·H 2 O} n (1), has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction analyses demonstrate that complex 1 exhibits a 2D bilayered structure interconnected with 4-bpda, resulting in 1D channels. These layers are arranged via the π···π stacking interactions between ptim ligands, forming a 3D supramolecular structure. The solid state luminescent property of 1 at ambient temperature was also investigated and showed a high selectivity and sensitivity for Fe(III) owing to the quenching effect. [ABSTRACT FROM AUTHOR]

A new two-fold interpenetrated zinc based metal–organic framework with dia topology has been isolated under hydrothermal conditions. Obtained complex can be used as a sensing material for the selective detection of nitro-aromatic compounds, especially for 4-nitroaniline that with high quenching constant and a low limit of detection. [Display omitted] • This study reports the successful assembly of a zinc-based MOF with a two-fold interpenetrating diamond-like 3D network. • This MOF demonstrates the ability to selectively detect NACs, particularly 4-NA with high quenching constant and sensitivity. • The sensing mechanism involves RET between NACs and MOF, while PET also contributes to the detection of 4-NA, 2-NP, and 4-NP. A zinc based metal-organic framework (MOF), namely, {Zn(L)·2H 2 O} n (1) {H 2 L = 4-(3,5-dicarboxyphenyl)-4,2′:6′,4′'-terpyridine}, has been successfully assembled in a hydrothermal environment. The single-crystal X-ray diffraction demonstrate that the structure of complex 1 features a two-fold interpenetrating diamond-like 3D network with four-connected dia topology. Luminescent sensing research shows that 1 can selectively detect nitro-aromatic compounds (NACs), especially for 4-nitroaniline (4-NA) that with high quenching constant (K SV = 1.66 × 104 M−1) and low limit of detection (LOD: 36.97 μM). The sensing mechanism of NACs by 1 may come from the resonance energy transfer (RET) between substrate and sensor; however, for 4-NA, 2-NP, and 4-NP, photo-induced electron transfer (PET) also exists. Importantly, after five cycles detection test the sensing capability of 1 does not exhibit significant decrease confirms that 1 possesses high stability and good recyclability. [ABSTRACT FROM AUTHOR]

[Display omitted] • Coordination bonds enable tailored drug delivery. • MOFs: Efficient drug loading, adaptive nanocarriers. • Metal-liganded Bioactives for controlled release. • Supramolecular assemblies: Targeted Cancer therapy. Stimuli-responsive drug delivery systems exhibit dynamic responses to pH, enzyme, redox, magnetic, thermal, and light stimuli through reversible coordination bonds with metal ions (e.g. Zn2+, Cu2+, Fe2+/Fe3+) and ligands such as ethylenediamine tetraacetic acid and azobenzene. Overcoming the limitations like uncontrolled release and degradation, coordination bonds offer tunability and dynamic responses for tailored drug delivery with a bond strength of 25–95 % of covalent bond. Metal organic frameworks (MOFs) utilize electrostatic interactions to demonstrate controlled drug release with significant adaptability and multifunctionality in pharmaceutical nanocarrier systems. Notably, MOFs like Fe-BTC and Zn-BTC exhibited higher drug-loading efficiencies of maximum 83 % and 92 %, respectively. Coordination polymers and MOFs with lanthanides explore the applications from self-healing materials to anticancer-metallogels. Metal-liganded bioactives (including iron-sulfur coordination complexes) enable controlled release of drug in response to stimuli like pH and ion activation. Mesoporous materials offer biocompatibility with better drug delivery efficiency, mainly for BCS class II and IV drugs. Supramolecular coordination complexes and coordination polymer networks with their high surface areas and pH-responsiveness behaviours explore tailored drug release profile. In liver cancer therapy, supramolecular assemblies demonstrated controlled drug release in response to stimuli of tumor microenvironment. pH/ROS-responsive nanoparticles showed a remarkable reduction in pro-inflammatory cytokines, primarily IL-6, reduced by 120-times. These advancements underscore the potential of coordination bond for enhancing the efficacy of drug in delivery system. The review article highlights the promise of metal–ligand interactions in drug design as well as emphasizes on the advancement of metal-coordinating drugs for approaching various pharmaceutical applications in the management and treatment of cancer, arthritis and inflammation. [ABSTRACT FROM AUTHOR]

Cd(II) complex 1 , namely {[Cd(HL)]·CH 3 OH} n was design as a new fluorescence probe for measuring concentration of Cu2+ ion in aqueous solution. Complex 1 is a 3,6-connected double-layered porous metal–organic framework, which was synthesized by optimizing the ratio of Cd(OH) 2 and a new ligand 4'-(((1-carboxyethyl)amino)methyl)-[1,1′-biphenyl]-3,5-dicarboxylic acid (H 3 L) under solvothermal conditions. It not only had good thermal and solvent stabilities, but also displayed a strong solid-state fluorescence centered at 375 nm with a moderate quantum yield of 37.12% under excitation at 275 nm. More importantly, its fluorescence could be obviously quenched by the addition of Cu2+ ion. The fluorescence quenching may be caused by the weak coordination interaction between Cu2+ and the uncoordinated imino N in ligand (HL)2–, as well as the slightly competitive absorption of excitation light by Cu2+. In the low concentration range of Cu2+ ion, the fluorescence quenching efficiency of complex 1 is closely related to the concentration of Cu2+ ion, and the relationship between fluorescence quenching efficiency and the concentration of added Cu2+ ion could be well fitted by Stern-Volmer equation with K SV being 1.589 × 104 M−1 and the detection limit for Cu2+ ion being 5.7 μM. Our case may provide potential applications for the detection of Cu2+ ion in daily domestic water. A new double-layered porous metal‒organic framework prepared by the solvothermal reaction of an amino acid-functionalized aromatic tricarboxylic acid ligand and Cd(OH) 2 displays good thermal stability, solvent stability, and strong fluorescence emission, and can be used as a highly sensitive water-stable fluorescence probe for detecting Cu2+. [Display omitted] • Amino acid-functionalized aromatic tricarboxylic acid ligand. • Double-layered metal-organic framework based on binuclear subunit [Cd 2 (COO) 4 ]. • Water-stable fluorescence probe of Cu(II). [ABSTRACT FROM AUTHOR]

• Three 2D to 3D metal-organic frameworks (MOFs) bearing mixed ligands were synthesized and characterized. • It is interesting to notice that three MOFs exhibit two excitation and one emission. • Each of the excitation of the sensor exhibit specific preference towards the quenchers (230 nm for nitenpyram and 290 nm for imidacloprid). The synthesis and characterization of three 2D to 3D metal-organic frameworks (MOFs) with mixed ligands, namely {[Cd(DINT)(TPA)(H 2 O)]ACN} n (BAO24) (H 2 TPA = tere phthalic acid, DINT = 1,4-di(imidazol-1-yl)naphthalene, and ACN = acetonitrile), {[Cd(DINT)(IPA)]DMF} n (BAO25) (H 2 IPA = iso phthalic acid and DMF = N,N -dimethylformamide), and [Cd(DINT)(PA)] n (BAO26) (H 2 PA = phthalic acid), were reported herein. The structures and purities of the MOFs were revealed and confirmed by single-crystal X-Ray diffraction, Fourier transform infrared spectroscopy, powder X-Ray diffraction, thermogravimetric analysis, and elemental analysis. The MOFs exhibited a fluorescence emission peak around λ em = 340 nm with relative excitation wavelengths at both 230 and 290 nm. Since the MOFs showed similar fluorescence properties, BAO24 was selected as a representative MOF in the fluorescent sensing processes. The result showed that BAO24 exhibited a high sensitivity for vitamin B2. However, when sensing pesticides, the sensor performed differently at each excitation wavelength. At λ ex = 230 nm, the sensor was quenched the most significantly with the nitenpyram analyte, while at λ ex = 290 nm, the highest fluorescence quenching was achieved by the imidacloprid analyte. [ABSTRACT FROM AUTHOR]

Two fresh Co(II)-based coordination polymers (CPs) have been synthesized and hydrogels loaded with Co(II) metal–organic frameworks of bleomycin were produced on the basis of the drug's sluggish release. Their application values were assessed on osteosarcoma cells, and the associated mechanism was investigated. [Display omitted] • Two fresh Co(II)-based coordination polymers (CPs) have been synthesized. • HA/CMCS hydrogel was prepared by chemical synthesis. • We designed and synthesized two metallogel particle frameworks encapsulating bleomycin drugs. • We compared the effects of the two metallogel particle frameworks for the treatment of hemangiomas. In the current paper, through utilizing two symmetrical pentacarboxylate ligands, namely, 3,5-di(2′,5′-dicarboxylphenyl)benzoic (H 5 L 1) and 3,5-di(2′,4′ dicarboxylphenyl)benzoic acid (H 5 L 2), two fresh Co(II)-basd coordination polymers (CPs), [Co 5 (μ 3 -H 2 O) 2 (L1) 2 ]·3DMA·4H 2 O (1 , DMA is N, N -dimethylacetamide) along with [Co 3 (μ 3 -OH)L2(H 2 O) 3 ]·H 2 O (2) have been synthesized under the conditions of solvothermal. With hyaluronic acid (HA) and carboxymethyl chitosan (CMCS) as raw materials, HA/CMCS hydrogel was prepared by chemical synthesis and its internal microstructure was observed by scanning electron microscope. Using bleomycin as a drug model, we designed and synthesized two metallogel particle frameworks encapsulating bleomycin drugs and compared the effects of the two metallogel particle frameworks as drug carriers for delivering bleomycin drugs for the treatment of hemangiomas. [ABSTRACT FROM AUTHOR]

Throughout the past ten years, metal-organic frameworks (MOFs) represent a class of coordination polymers characterized by high porosity and structural flexibility, and are increasingly used in biochemical analysis. However, largely due to the extremely low content of biomolecules, the transferability and support between MOFs material and sensing substrate are crucial for sensing sensitivity and stability, which directly affect their practical applications. Rapid in-situ MOF synthesis strategy is very important, which usually involves the direct growth of MOFs onto the sensing substrate in a "one-pot" process for simple, fast, portable and ideally large-scale preparation. This review focuses on the most current developments in the field of using MOFs produced quickly in-situ for highly sensitive detection of tiny amounts of protein, glucose, dopamine, ascorbic acid and uric acid by electrochemical, fluorescence, Raman, colorimetric sensing and microfluidics techniques. • The recent advances of rapid in-situ synthesis strategy for MOF synthesis. • Rapid in-situ synthesis of MOFs for biosensing by electrochemistry, spectrochemistry and microfluidics. • In-situ synthesized MOFs for detecting diverse biomolecules including protein, glucose, dopamine, ascorbic acid and uric acid. • The current challenges and future prospects of this topic. [ABSTRACT FROM AUTHOR]

The antimicrobial properties of 8-Hydroxyquinoline (8-Hq), a small organic compound known for its metal-chelating capabilities, hold significant promise. However, its limited solubility in water poses a challenge for practical applications. In this study, we address this limitation by augmenting the antimicrobial efficacy of 8-Hq through its integration into the metal-organic framework UiO-66 (named 8-Hq@UiO-66) and coupling it with iron ions (designated as Fe/8-Hq@UiO-66) via an adsorption process. The sorption isotherm and adsorption kinetics were meticulously examined using Langmuir's adsorption model and the pseudo-second-order kinetic model. Material characterization techniques including powder X-ray powder diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption isotherms, ultraviolet–visible spectroscopy, and photoluminescence spectroscopy revealed the coordination of zirconium clusters and iron with the nitrogen and hydroxyl groups of 8-Hq, respectively. Furthermore, our investigation into metal ion adsorption demonstrated that the 8-Hq@UiO-66 composite displayed a notable selectivity for iron ions over other metal ions in aqueous media. Under optimized conditions, the adsorption capacity for iron ions ranged from approximately 34–46 mg g−1. Importantly, the Fe/8-Hq@UiO-66 composite exhibited potent antimicrobial activity against Bacillus subtilis , Staphylococcus aureus , and Escherichia coli. These findings underscore the potential of incorporating 8-Hq into porous metal-organic frameworks and coupling it with iron ions to enhance its antimicrobial efficacy. [Display omitted] • Enhanced antimicrobial efficacy via 8-Hq and iron ion integration into UiO-66. • Insights from sorption isotherms and kinetics models. • Selective conjugation of iron ions by 8-Hq@UiO-66. • Potent antimicrobial activity against diverse bacterial strains demonstrated. [ABSTRACT FROM AUTHOR]

In this study, a new compound 1 with the formula as [Cd((S/R)-ptz) 2 ] n was solvothermal synthesized from Cd(II) salt and (S/R)-5-(pyrrolidin-2-yl)-1H-tetrazole ((S/R)-ptzH) ligand. Compound 1 exhibits good solvent stability and acid-base stability. Notably, 1 displays yellow room-temperature phosphorescence that can be visually observed for approximately 2 s, marking a significant milestone in metal-organic frameworks (MOFs) incorporating proline-tetrazole ligand. Presented here is a new room-temperature phosphorescent Cd-MOF with 2 s long afterglow. [Display omitted] • A new Cd-metal-organic framework based on proline-tetrazole exhibits excellent solvent stability and acid-base stability. • It displays yellow room-temperature phosphorescence (RTP) that can be visually observed for approximately 2 s. • It marks a significant milestone in MOFs incorporating proline-tetrazole ligand. [ABSTRACT FROM AUTHOR]

Porous coordination polymers, alternatively identified as metal-organic frameworks (MOFs) nanoparticles, are becoming more and more important in the field of nanomaterials science, especially in catalysis. The intricate structures of MOFs enable the integration of metal nodes, encapsulating substrates, and functional linkers, facilitating synergistic engineering. This study underscores the importance of Ni-MOFs in synthetic chemistry, particularly their role in organic compound synthesis. It investigates their utility in oxidation, hydrogenation, coupling reactions, C-H activation, and N-heterocyclic compound generation. Ni-MOFs, functioning as well-defined heterogeneous catalysts are pivotal in addressing societal challenges across synthesis, energy, and environmental domains. Despite notable achievements, there remains a significant need for further advancements to deepen our understanding of these processes beyond initial demonstrations, especially concerning the synthesis of bioactive compounds. This focused examination of Ni-MOFs is anticipated to offer valuable insights for future research endeavors exploring MOF catalytic applications. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • A new manganese MOF is synthesized and fully characterized. • The MOF shows interesting ferrimagnetic behavior. • The MOF can efficiently catalyze cycloaddition of CO 2 with epoxides to cyclic carbonates. A new three-dimensional (3D) metal–organic framework (MOF) [Mn 3 (bqca) 2 (DMF) 4 ] n (1) is constructed based on a tricarboxylate ligand 2,3-di-(4-carboxyphenyl)-quinoline-6-carboxylic acid (H 3 bqca) through solvothermal reaction. The structure, composition and stability of the complex were fully characterized by single crystal X-ray diffraction, powder X-ray diffraction, infrared spectrum and thermogravimetric analysis. The results show that 1 has a 3D microporous framework and exhibits high thermal stability up to 450 ℃. Direct-current magnetic susceptibility reveals that 1 is a rare ferrimagnetic homospin system. Importantly, 1 can effectively catalyze the cycloaddition reaction of CO 2 with epoxides to generate cyclic carbonates with high yields and selectivity, and it can also be recycled at least five times without a noticeable change in catalytic efficiency. [ABSTRACT FROM AUTHOR]

• Structural features of lanthanide coordination polymers are reviewed. • Crystal structures of lanthanide coordination polymers are provided. • Coordination environment of lanthanides is discussed. • The role of lanthanides in modulating the structural pattern is revealed. • Catalytic applications of lanthanide coordination polymers are highlighted. The review showcases the structural features of an array of recently reported lanthanide coordination polymers with catalytic properties. The field of lanthanide coordination polymers has considerably progressed during the last decade placing it at the forefront of the materials science. The wealth of obtained data clearly demonstrates that lanthanides play a determinant role in tailoring the structural pattern, coordination environment, dimensional configuration and network architecture of coordination polymers. As a rule, the lanthanide(III) ions possess a high coordination number and a large atomic radius, and because of that they tend to generate highly connected complex structures with different coordination geometry. In this way, they easily build two-dimensional and three-dimensional architectures with definite channels and permanent pores. Owing to their strong oxophilic propensity and hard Lewis acid character, lanthanides effectively succeed in creating robust, stable coordination polymers and MOF structures and viable matrices via strongly binding the coordinating groups of the accurately selected organic linkers. Such unique particularities involve a distinct morphology, diverse crystal structures, uniform porosity, a defined pore size and shape, precisely controlled number and dimensions of channels. Their specifically designed configurations allow the access of guest molecules and a controlled distribution of the metal ions on the surface or within the network. Additionally, the lanthanide ions afford new synergistic Lewis acid sites beneficial for productive catalytic applications. These attractive capabilities of lanthanide coordination polymers enabled them to be fruitfully used as sustainable and recyclable heterogeneous catalysts in diverse organic transformations. like carbon-carbon bond forming, Strecker reaction, CO 2 cycloaddition, Knoevenagel condensation, hydroboration and cyanosilylation. [ABSTRACT FROM AUTHOR]

[Display omitted] • A Cd(II) MOF features 1D channels and rich oxygen sites; • High thermal and chemical stability for the Cd(II)-MOF; • The Cd(II)-MOF performs high CH 4 production from C 1 -C 3 mixtures; • The gases selectivity was elucidated by GCMC simulations and first-principle DFT calculations. Metal-organic frameworks (MOFs) have garnered increasing attention for their effective separation of light hydrocarbons owing to their prominent separation selectivity and energy-efficient adsorption process. Here, we constructed a robust stable ultramicroporous Cd(II)-MOF ([Cd 5 (NTA) 4 (H 2 O) 2 ] (Me 2 NH 2 +) 2 ·10H 2 O (1)) with abundant accessible oxygen sites and investigated its adsorption performance for recovering high-purity methane (CH 4) from natural gas (NG) including C 1 (CH 4)/C 2 (C 2 H 6)/C 3 (C 3 H 8) mixtures. At ambient conditions, the theoretical equilibrium separation selectivity of 1 for C 2 H 6 /CH 4 (v/v = 10/85) and C 3 H 8 /CH 4 (v/v = 5/85) were found to be 34.3 and 223.8, respectively. The CH 4 /C 2 H 6 /C 3 H 8 (v/v/v = 85/10/5) mixture breakthrough experiments for 1 , conducted at 298 K, demonstrated effective separation performance with breakthrough times of up to 136 and 280 min·g−1 for C 2 H 6 and C 3 H 8. Particularly, the CH 4 productivity (purity > 99.9 %) with 9.8 mmol·g−1 ranked the third in reported literatures, lower to the reported maximum value of 13.28 mmol·g−1 for Ni(TMBDC)(DABCO) 0.5. Furthermore, Grand Canonical Monte Carlo (GCMC) simulations and first-principles density functional theory (DFT) calculations revealed that the high uptake and selectivity for C 3 H 8 and C 2 H 6 can be attributed to the abundant oxygen sites present in the pores. The dynamic breakthrough experiments comprehensively demonstrated that the proposed MOF can be an effective potential adsorbent for the practical separation of CH 4 /C 2 H 6 /C 3 H 8 mixtures. [ABSTRACT FROM AUTHOR]

• Three alkaline earth-based MOFs were synthesized under hydrothermal conditions. • Compounds 1-3 reveal structural diversity owing to different metal ions and organic ligands. • The luminescent properties of compounds 1 - 3 were studied in detail. The alkaline earth-based metal-organic frameworks (MOFs) have attracted more and more attention for their beautiful structure and environmental friendliness. In this work, three alkaline earth-based MOFs, namely [Ba(HL 1)] n (1), [Ca(HL 1)(H 2 O) 2 ] n (2), and [Ba(HL 2)] n (3) (H 3 L 1 = 1-(3-carboxyphenylmethyl)-1H-pyrazol-3,5-dicarboxylic acid and H 3 L 2 = 1-(4-carboxyphenylmethyl)-1H-pyrazol-3,5-dicarboxylic acid), were synthesized under hydrothermal conditions. Compounds 1-3 reveal structural diversity owing to different metal ions and organic ligands. Thermal and solvent stability were characterized by thermogravimetric analyses (TG) and powder X-ray diffraction (PXRD), respectively. The solid-state luminescent properties were also investigated. The result shows a clear correlation between emission bands and excitation wavelengths of compounds 1-3. Three new alkaline earth-based metal-organic frameworks with luminescent properties were synthesized and characterized. [Display omitted] [ABSTRACT FROM AUTHOR]

Three novel MOFs were synthesized as Fenton-like catalysts to degrade Rhodamine B with high efficiency, stability and recyclability. [Display omitted] • Three novel MOFs were synthesized with good stability and recyclability as Fenton-like catalysts. • 1–3 can photocatalytic degrade Rhodamine B with high efficiency. • The Fenton-like photocatalytic degradation mechanism of 1–3 was explored. Three novel metal organic frameworks (MOFs) including {[Zn 3 (nip) 3 (TPPA) 3 ]·3 DMF·H 2 O} n (1), [Co(NH 2 -bdc)(TPPA)(H 2 O)] n (2) and [Cd 2 (NH 2 -bdc) 2 (TPPA) 2 ] n (3) (TPPA = tri(4-pyridylphenyl)amine, H 2 -nip = 5-Nitroisophthalic acid, NH 2 -bdc = 2-Aminoterephthalic acid) were successfully prepared under hydrothermal conditions. X-ray single crystal analyses revealed that MOFs 1 – 3 possess 3D architecture. Impressively, all of them can function as a highly photocatalyst for degradation of Rhodamine B (RhB) dye under low-energy irradiation of a 150 W Xenon lamp. Moreover, the photocatalytic performance is significantly improved after the addition of H 2 O 2 , which could be attributed to their high efficiencies in generating OH and O 2 − radicals. In addition, MOFs 1–3 showed very stable activity in the degradation of RhB, and showed no significant loss of activity after three consecutive uses. [ABSTRACT FROM AUTHOR]

A natural polysaccharide-based vehicle is facilely prepared for enantioselective loading of S-naproxen (S-NPX) and its programmed release. Cyclodextrin metal-organic frameworks (CD-MOF) are synthesized through the coordination of K+ with γ-cyclodextrin (γ-CD). Compared with R-NPX, the CD-MOF preferably combines with S-NPX, which can be confirmed by the thermodynamic calculations. The S-NPX loaded CD-MOF (CD-MOF-S-NPX) is grafted with disulfide bond (–S–S–) to improve its hydrophobicity, and the loaded S-NPX is further encapsulated in the chiral cavity of γ-CD by carboxymethyl potato starch (CPS) hydrogels. The intermolecular hydrogen bonding of the CPS hydrogels is prone to be destroyed in mildly basic media (∼pH 8.0), resulting in the swelling of the hydrogels; the –S–S– linkage in the vehicle can be cleaved in the presence of glutathione (GSH), leading to the collapse of the CD-MOF. Therefore, the programmed release of S-NPX can be achieved. Also in this work, the release kinetics is investigated, and the results indicate that the release of S-NPX is controlled by the Higuchi model. • A γ-CD-based vehicle is facilely prepared for chiral separation of the NPX isomers. • The CD-MOF-S-NPX is grafted with –S–S– bond to improve the hydrophobicity. • The loaded S-NPX is further encapsulated by the CPS hydrogels. • Programmed release of S-NPX from the SS-CD-MOF-S-NPX-gel is achieved. • Release kinetics reveals that the release of S-NPX is controlled by Higuchi model. [ABSTRACT FROM AUTHOR]

• Hydrothermal synthesis of the same structure of Co-/Ni-based MOFs. • Mixed-ligand Co-/Ni-based MOFs by introduction of 4-bpd ligand can be used to degrade crystal violet in Fenton-like system. • The Co-based MOFs have better photocatalytic/electrocatalytic capacity than their isostructural Ni-based MOFs. • The oxygen evolution reaction (OER) properties of four MOFs were studied. Four MOFs with two identical structures were constructed by using 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (4-bpd) and 1,3-dicarboxyadamantane (H 2 adc) as linkers, and Co2+, Ni2+ as metal nodes by solvothermal method. Single-crystal X-ray diffraction revealed that complexes [Co 2 (adc) 2 (4-bpd)] n (1) and [Ni 2 (adc) 2 (4-bpd)] n (2) have the same two-dimensional molecular structure, while complexes [Ni(Hadc) 2 (H 2 O) 2 ] n (3) and [Co(Hadc) 2 (H 2 O) 2 ] n (4) exhibit identical one-dimensional chain-like molecular structures. The photo/electrocatalytic performances and thermal stability of four complexes were investigated. Introducing 4-bpd to form mixed-ligand complexes 1 and 2 enables the degradation of crystal violet (CV) dye in a Fenton-like system. Furthermore, there is an improvement in the oxygen evolution reaction (OER) catalytic performance among the MOFs of the same metal nodes. It is worth mentioning that in this study, Co-based MOFs showed better catalytic performance than Ni-based MOFs, which is mainly attributed to the distinctive electronic structure of Co2+ and Ni2+ d orbitals. [Display omitted] [ABSTRACT FROM AUTHOR]

Smart iron-based metal–organic framework MIL-101(FeIII) nanovehicles gated with CuII-tannic acid (TA) coordination polymers were constructed via "on site" self-assembly. The controlled release of antitumor drugs encapsulated within MIL-101(FeIII) mesopores was realized in response to the tumor microenvironments [such as low pH, glutathione (GSH), H 2 O 2 , and adenosine-5'-triphosphate (ATP)] and near infrared light, due to the photothermal effect of the nanocarriers, by the disassembly of the CuII-TA gating films and/or the degradation of the MIL-101(FeIII) nanocarriers. The low pH gave rise to the disassembly of the CuII-TA gating films and the release of drugs. The competitive coordination of ATP with CuII/FeIII caused the disassembly of the CuII-TA gating films, the degradation of the nanocarriers, and the release of drugs. The overexpressed GSH could reduce CuII/FeIII to CuI/FeII and resulted in the disassembly of the CuII-TA gating films and the degradation of the nanocarriers, and the produced CuI/FeII could catalyze H 2 O 2 of elevated level to generate more hydroxyl radicals via the Fenton/Fenton-like reactions for cell apoptosis. The cascade reactions of the depletion of GSH and the generation of hydroxyl radicals based on the gated nanovehicles achieved chemodynamic therapy (CDT) besides chemotherapy. The smart nanovehicles have promising applications in combination tumor therapy of chemotherapy and CDT. [Display omitted] • Construction of smart Fe-MOF nanovehicles gated with CuII-tannic acid gatekeepers. • Good photothermal stability of nanovehicles and generation of reactive oxygen species. • Multiple stimuli-responsive controlled release of loaded drugs and mechanisms. • Intracellular drug release, cell viability, and apoptosis of nanovehicles. [ABSTRACT FROM AUTHOR]

• Two new 3D Cd(II)/Co(II) MOFs based on binuclear clusters are described. • MOFs 1 and 2 display as 6-connected mab and bsn networks. • Both MOFs exhibit selective sensing toward Fe3+, Cr 2 O 7 2− and nitrobenzene. Two novel three-dimensional (3D) Cd(II)/Co(II) metal-organic frameworks (MOFs), [Cd 2 (seb) 2 (bbmb)(H 2 O) 2 ] n (1) and {[C o 2 (seb) 2 (bbmb) 2 (H 2 O)]·0·5H 2 O} n (2), were synthesized under hydrothermal conditions based on sebacic acid (H 2 seb) and 4,4′-Bis(benzimidazol-1-ylmethyl) biphenyl (bbmb) ligands. Their crystal structures were structurally characterized by single-crystal X-ray diffraction. MOFs 1 and 2 both show a 3D framework based on binuclear Cd 2 or Co 2 clusters, respectively. In 1, the Cd 2 clusters are linked by seb2- into a 2D corrugated layer. These layers are further connected by bbmb to generate a 3D structure with 6-connected (44·610·8) mab topology. In 2, the Co 2 clusters form a 1D chain through the bbmb ligands, the chains are linked by seb2− into a 3D framework with 6-connected (48·54·63) bsn topology. Fluorescence sensing experiments show that 1 and 2 have good ability for detection of Fe3+, Cr 2 O 7 2− and nitrobenzene (NB) with low detection limits as 5.83 μ M, 1.36 μ M and 2.70 × 10−7M for 1 and 6.19 μ M, 1.40 μ M and 2.90 × 10−7M for 2, respectively. Furthermore, the sensing mechanism was also investigated in detail by various detection means and theoretical calculations. Two new 3D Cd(II)/Co(II) MOFs of 4,4′-Bis(benzimidazol-1-ylmethyl) biphenyl and sebacic acid are described. MOFs 1 and 2 display as rarely reported 6-connected mab and bsn topologies based on the binuclear units. Both MOFs were confirmed to be luminescent sensors for Fe3+, Cr 2 O 7 2− and nitrobenzene. [Display omitted] [ABSTRACT FROM AUTHOR]

• Two new 3D Cd(II)/Co(II) MOFs based on binuclear clusters are described. • MOFs 1 and 2 display as 6-connected mab and bsn networks. • Both MOFs exhibit selective sensing toward Fe3+, Cr 2 O 7 2− and nitrobenzene. Two novel three-dimensional (3D) Cd(II)/Co(II) metal-organic frameworks (MOFs), [Cd 2 (seb) 2 (bbmb)(H 2 O) 2 ] n (1) and {[C o 2 (seb) 2 (bbmb) 2 (H 2 O)]·0·5H 2 O} n (2), were synthesized under hydrothermal conditions based on sebacic acid (H 2 seb) and 4,4′-Bis(benzimidazol-1-ylmethyl) biphenyl (bbmb) ligands. Their crystal structures were structurally characterized by single-crystal X-ray diffraction. MOFs 1 and 2 both show a 3D framework based on binuclear Cd 2 or Co 2 clusters, respectively. In 1, the Cd 2 clusters are linked by seb2- into a 2D corrugated layer. These layers are further connected by bbmb to generate a 3D structure with 6-connected (44·610·8) mab topology. In 2, the Co 2 clusters form a 1D chain through the bbmb ligands, the chains are linked by seb2− into a 3D framework with 6-connected (48·54·63) bsn topology. Fluorescence sensing experiments show that 1 and 2 have good ability for detection of Fe3+, Cr 2 O 7 2− and nitrobenzene (NB) with low detection limits as 5.83 μ M, 1.36 μ M and 2.70 × 10−7M for 1 and 6.19 μ M, 1.40 μ M and 2.90 × 10−7M for 2, respectively. Furthermore, the sensing mechanism was also investigated in detail by various detection means and theoretical calculations. Two new 3D Cd(II)/Co(II) MOFs of 4,4′-Bis(benzimidazol-1-ylmethyl) biphenyl and sebacic acid are described. MOFs 1 and 2 display as rarely reported 6-connected mab and bsn topologies based on the binuclear units. Both MOFs were confirmed to be luminescent sensors for Fe3+, Cr 2 O 7 2− and nitrobenzene. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • The advent of MOF for applications in VOCs detections is highlighted herein. • MOFs are thoroughly explored, restricting the application to VOCs detection. • MOFs performances in VOCs detection are here described in relation to their structures. • MOFs and bio-MOFs have shown promising prospects in the detection of VOCs. Volatile organic compounds (VOCs) are present in the mixture of gases found in the exhaled human breath. Since their occurrence in the breath may indicate the presence of a disease, some VOCs are referred to as "biomarkers." One of the most interesting types of gas sensors which have been thoroughly explored for VOCs detections is based on metal–organic frameworks (MOFs), which are crystalline porous coordination polymers assembled by following reticular chemistry rules. The aim of this review is to present a comprehensive summary of the latest MOF-derived composites that have been employed as VOCs biomarkers' sensors. The study will first focus on reviewing the role of VOCs as disease biomarkers and then on the most prevalent methods used for analyte sensing by MOFs, including optical, electromechanical, and electrical sensing. The successive section examines some of the most recent reports on the use of five typical MOF families for sensing VOCs relevant as disease biomarkers. The basic structural features of these MOFs and their fundamental working principles as gas sensors will be highlighted in each sub-section through selected examples, emphasizing at the same time the correlation between the MOFs structure and functionalities, and their sensing properties. Finally, the study will be concluded with a discussion about a new class of MOFs called bio-MOFs, and their potentialities in VOCs sensing. [ABSTRACT FROM AUTHOR]