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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]

Five Metal–Organic Frameworks ({[M2(tdc)2(L)2]·2DMF}, tdc = 2,5-thiophenedicarboxylate, M = ZnII (1–Zn), CuII (1–Cu), MnII (1–Mn), {[Zn(oba)(L)]·DMF·H2O} (2–Zn), oba = 4,4′-oxybisbenzoate, and {[Zn2(bpdc)2(L)2]·L}, (3–Zn) bpdc = 4,4′-biphenyldicarboxylate) that incorporate the redox-active 2,5-dipyridylthiazolo[5,4-d]thiazole (DPTzTz) ligand (L) have been synthesised and their electronic properties elucidated. The ligand-based organic radicals were generated using in situ techniques and monitored using a suite of solid-state spectroelectrochemistry techniques. The absence of a near infra-red band (NIR), indicating through-space intervalence charge transfer (IVCT), in all analysed materials suggests that both the inter-ligand distance between cofacial TzTz moieties and the flexibility of the TzTz moiety affect the through-space IVCT. [ABSTRACT FROM AUTHOR]

A 3D Co-based metal–organic framework has been prepared, which contains a bis(triarylamine) with terphenyl units as a redox-active linker. Manipulation of the redox events via the electrochemical method confirmed that charge hopping is dominant within the 3D framework. Investigation of the in situ spectroelectrochemical properties within the structure leads to the formation of mono and dual radical cations obtained reversibly in two-steps due to the presence of two redox-active sites. [ABSTRACT FROM AUTHOR]

The combination of electron-deficient viologen ligands with electron-rich POMs is a typical acceptor–donor system that has recently received much attention. Under solvothermal and hydrothermal conditions, by introducing three symmetric viologen ligands into POM-based hybrid materials, we successfully constructed four POMs–viologen inorganic–organic hybrid compounds, namely (1,3-bcbpy)2·(δ-Mo8O26) (1) (1,3-bcbpy·2Cl = 1,1′-bis(3-carboxybenzyl)-4,4′-bipyridine dichloride), {CoII(1,4-bcbpy)2(H2O)2[H2(β-Mo8O26)]}·2H2O·2CH2O (2), (1,4-bcbpy)2·(δ-Mo8O26)·2H2O (3) (1,4-bcbpy·2Cl = 1,1′-bis(4-carboxybenzyl)-4,4′-bipyridine dichloride, CH2O = formaldehyde), and {CuII(1,1-pmbby)2(H2O)[H2(β-Mo8O26)2]}·5H2O·C2H7N (4) (1,1-pmbby·2Cl = 1,1′-[1,4-phenylbis(methylene)]bis-(4,4′-bipyridine)dichloride, C2H7N = dimethylamine). These four compounds exhibit different fascinating structures, especially compound 4 is a typical metal–organic framework. Compounds 1–4 exhibit good discoloration behaviors under various external stimuli. For example, compounds 1–4 showed a positive response to the irradiation from a 300 W Xe lamp. When a positive voltage was applied to the ECD based on compounds 1–4, 1/2/3/4-ECD underwent a significant color conversion. What's more, compound 4 also showed obvious discoloration results after heating. In a word, 1–4 are multifunctional discoloration materials under different external stimuli. In addition, the coated filter paper prepared based on compound 3 can be used as a new printing material medium and can be successfully applied in erasable inkless printing and dual anti-counterfeiting. [ABSTRACT FROM AUTHOR]

Three new two‐dimensional metal‐organic frameworks (MOFs), namely [Cu3(NDIC)3 ⋅ C2H5OH ⋅ 2H2O]n (1), [Co2(NDIC)2 ⋅ 2 C3H7NO ⋅ H2O]n ⋅ nC2H5OH (2) and [(Zn3O)2(Zn(H2O)4)(NDIC)6 ⋅ C3H7NO ⋅ C2H5OH ⋅ C2H5O ⋅ 7H2O]n (3) based on the ligand 5‐norbonene‐2,3‐dicarboximide isophthalic acid (H2NDIC) have been synthesized under solvothermal condition, which have been further characterized by single crystal X‐ray diffraction analysis, powder X‐ray diffraction (PXRD) elemental analysis, ICP, TG and FT‐IR spectroscopy. The ligand displayed distinctive coordination modes to connect mononuclear metal ion, binuclear and trinuclear metal clusters to generate different 2D layered structures in compound 1–3. Compound 1 shows KGM type network based on paddle‐wheel Cu2(COO)4 as secondary building units (SBUs). Compounds 2 and 3 have the undulating 2D (4, 4) SQL topology with the point symbol (44 ⋅ 62) based on Co2(COO)4 and Zn3(μ3‐O)(COO)4 as SBUs, respectively. The magnetic properties of compound 1–2 and the luminescent property of compound 3 and its fluorescent detection for Fe3+ has been investigated and discussed. [ABSTRACT FROM AUTHOR]

New metal-organic coordination polymer Cd[H2L] (I) (where H4L is 4,4'-([2,2'-bipyridine]-6,6'-diylbis(oxy))diphthalic acid) is synthesized in a high yield under the solvothermal synthesis conditions. According to the X-ray diffraction (XRD) data, each Cd(II) cation binds four organic ligands: one ligand is bound via the coordination of the chelate bipyridyl fragment, two ligands are linked via the bidentate coordination of the deprotonated COO groups, and one ligand is bound via the monodentate coordination of the protonated carboxylate group. The synthesized three-dimensional metal-organic framework contains no free space capable of including guest molecules. Compound I is characterized by powder XRD, IR spectroscopy, and elemental (C, H, N) and thermogravimetric analyses. The luminescence spectra of compound I are recorded. [ABSTRACT FROM AUTHOR]

A UiO-67-type Zr-based metal–organic framework (MOF) with dibenzothiophene linkers, UiO-67-S, was synthesized using a solvothermal method. The crystal structure of UiO-67-S exhibits the same topological structure as UiO-67 and its derivatives. UiO-67-S shows high thermal stability and excellent permanent porosity. Moreover, its excellent hydrogen storage indicates that the thiophene moiety is suitable for enhancing the hydrogen storage ability of MOFs. [ABSTRACT FROM AUTHOR]

Non‐centrosymmetric metal–organic frameworks (MOFs) have recently emerged as a promising class of coordination polymers for nonlinear optics and light conversion. Nevertheless, achieving high endurance and efficiency for the light conversion within the whole visible range by a single crystal of MOF remains a challenge. This article reports on the design of two non‐centrosymmetric MOFs based on a 1,3,5‐benzenetricarboxylic acid ligand and Er/Co ions, providing an efficient and simultaneous multiple second and third optical harmonic generations (SHG, THG) from 400 to 750 nm with a high endurance (over 100 cycles or 3 h of continuous operation). Optical experiments and quantum chemical modeling of the MOF single crystals confirm the polarization and chemistry‐dependent efficiency of SHG and THG, associated with the varied MOFs' symmetry and dipole moment. The observed coherent light conversion within the whole visible range by MOF single crystals at ambient conditions makes it possible to achieve the multicolor (up to three) coherent emission required for modern laser technologies, making MOFs highly competitive and sustainable materials for nonlinear optics. [ABSTRACT FROM AUTHOR]

The incremental use of herbicides is now posing a pollution problem in aquatic systems. Therefore, it is necessary to decompose this class of harmful components existing in wastewater. Metal–organic frameworks (MOFs) are a peculiar class of multidimensional materials that can be employed as a photocatalyst to decompose pesticides present in the wastewater discharged. For this we have synthesized three high-stability Co(II)-based metal organic frameworks (MOFs) [Co(H2L)(bb)·DMF]n (1), [Co(L)0.5(bb)]n (2), and [NH2(CH3)2][Co2(μ3-OH)(L)(bb)] (3), where H4L = 5,5′-(1,2-phenylenebis(methyleneoxy)diisophthalic acid and bb = 4,4′-bis(imidazolyl)biphenyl. These MOFs are characterized by thermal analyses and single-crystal X-ray diffraction. 1 features a new 3D, 2-nodal 4,4-connected network with a Schläfli symbol of (44·62). 2 displays a 3D, 4,4-c network, with a Schläfli symbol (64·82). 3 shows a 3D two nodal (3,8) connected net with a Schläfli symbol (43)2(46·618·84). 1–3 are semiconducting in nature with Eg of 3.31 eV, 2.95 eV, and 3.25 eV, respectively. These three MOFs show high catalytic activities for the degradation of different pesticides, including four common pesticides thiabendazole (TBZ), dinotefuran (DTF), metamitron (MMT), and ciprofloxacin (CIP) in an aqueous solution. TBZ shows photocatalytic degradation by the synthesized MOF, which demonstrated 89% degradation. Moreover, the possible photodegradation mechanism was proposed and explored by a radical tapping experiment. The Hirshfeld surfaces study demonstrated that these synthesized coordination polymers contain various forms of intermolecular contacts (C⋯C, H⋯C, H⋯H, and O⋯H). [ABSTRACT FROM AUTHOR]

An ethynyl-modified interpenetrated MOF material with lvt topology, [Cu2(BTEB)(NMF)2]·NMF·8H2O (compound 1, H4BTEB = 4,4′,4′′,4′′′-(benzene-1,2,4,5-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, NMF = N-Methylformamide), was successfully synthesized by using an alkynyl-functionalized H4BTEB organic ligand under solvothermal conditions. Structural analysis shows that compound 1, consisting of a tetradentate carboxylic acid ligand and classical [Cu2(CO2)4] paddle-wheel structure building units, has a rare 4-connected lvt topology with dual interpenetrating structure, which can improve the framework stability, as well as the gas adsorption capacity and selectivity due to the restricted pore channel. According to the study of gas adsorption performance, compound 1 with a larger surface area, boasts a superior adsorption capacity for small gas molecules. Also, ideal adsorption solution theory (IAST) computational simulation shows that compound 1 has good gas adsorption selectivity for C3H8/CH4, indicating its potential application in gas separation. [ABSTRACT FROM AUTHOR]

A new metal-organic framework (MOF) [Co3(btdc)3(5,5′-dmbpy)2] • 5DMF (1) (H2btdc is 2,2′-bithiophene-5,5′-dicarboxylic acid and 5,5′-dmbpy is 5,5′-dimethyl-2,2′-bipyridyl) was synthesized. Compound 1 contains trinuclear secondary building blocks connected to each other by the btdc2− ligand to form a layered coordination polymer with a free accessible volume of 36%. [ABSTRACT FROM AUTHOR]

Three-dimensional coordination polymers Cat2[{Zn4O}2(H2O)2(2,5-I-bdc)7] (1) (2,5-I-bdc = 2,5-diiodoterephthalate, Cat is dimethylammonium) and [Zn2(2,5-I-bdc)2dabco] (2) (dabco is 1,4-diazobicyclo [2.2.2]octane) are prepared. The structures of 1 and 2 are determined by single crystal X-ray diffraction. It is shown that the structure of 2 has a halogen bond between guest DMF molecules and the MOF iodine atom. The I⋯O distances are 2.93-3.03 Å. [ABSTRACT FROM AUTHOR]

[Display omitted] Constructing Fe-Cu bimetal catalysts is an efficient strategy to promote Fe(III)/Fe(II) cycle, whereas there is still a long way to go before fully understanding the role of the Cu in the catalysts. Herein, a new Fe-MOF namely BUC-96(Fe) was fabricated from FeSO 4 ·7H 2 O, 4,4′-bipyridine (bpy) and 2,5-dihydroxyterephthalic acid (H 4 dhtp) by both hydrothermal reaction and microwave-assisted method. Also, bimetal BUC-96(FeCu-x) were obtained when the CuSO 4 was added into the system identical to the synthesis process of BUC-96(Fe). Series BUC-96 MOFs showed good organics elimination performance via Fenton-like process, where 88.1% (k = 0.0672 min−1) of chloroquine phosphate (CQ, 20 mg/L) was decomposed over pristine BUC-96(Fe) within 30 min. Interestingly, nearly 100% CQ was degraded over BUC-96(FeCu-5) as catalyst under the identical conditions within 5 min, whose reaction rate (1.3527 min−1) was 20.1-fold higher than that of BUC-96. Additionally, BUC-96(FeCu-5) exhibited excellent Fenton-like oxidation degradation performance for 10 selected emerging organic pollutants. The reaction mechanism was studied in detail by experiments, and density functional theory (DFT) calculation. The results revealed that the introduced Cu not only accelerated Fe(III)/Fe(II) cycles, hydroxyl radical (·OH) generation, electron transfer, but also lowered H 2 O 2 dissociated energy barrier. This work advanced the bimetal MOFs construction and application in wastewater treatment via Fenton-like process. [ABSTRACT FROM AUTHOR]

The optimisation of the crystallisation of the hydrothermally-stable metal–organic framework Yb6-MOF (Yb6(BDC)7(OH)4(H2O)4) to provide a reproducible one-step synthesis is achieved by use of the sodium salt of benzene-1,4-dicarboxylate (Na2BDC) as ligand precursor and control of pH with aqueous NaOH at 190 °C over 3 days. Phase purity is confirmed using powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). During exploration of synthesis conditions from the same set of chemical reagents, three further ytterbium benzene-1,4-dicarboxylates have been isolated and structurally characterised using single-crystal X-ray diffraction, with phase purity assessed by PXRD and TGA. UOW-3 (Yb2(H2O)6(BDC)3) crystallises by lowering pH, and has a relatively dense three-dimensionally connected structure with no Yb–O–Yb linkages but dimers of Yb bridged by BDC linkers lying in the ab plane with a pseudo, pillared-layered structure, where BDC connects along c. UOW-4 (Yb4(BDC)6(H2O)6) forms under the same chemical conditions but upon lowering the temperature to 100 °C, and this material again contains no Yb–O–Yb linkages, but chains of BDC-bridged Yb centres cross-linked to give a dense three-dimensional structure. Upon increasing pH of the synthesis mixture, the material UOW-5 forms, Yb5O(OH)8(BDC)2(HBDC), consisting of dense inorganic layers of ytterbium oxyhydroxide, cross linked by BDC and HBDC pillars. The formulation is supported by infrared spectroscopy, which provides evidence for the HBDC monoanion, and also the presence of a short O–O distance indicative of hydrogen bonding between a carboxylate OH and an oxide anion of the inorganic layer. UOW-3 and UOW-4 both convert to Yb6-MOF upon heating in water above their synthesis temperature, whereas UOW-5 is hydrothermally stable at 240 °C. The structures of the new materials are discussed in terms of ligand binding modes, and connectivity of metal centres, with comparison to other reported Yb-BDC phases in order to relate structural chemistry to their synthesis conditions and the hydrothermal stability of the materials. [ABSTRACT FROM AUTHOR]

Owing to their mechanical resilience and non-toxicity, titanium implants are widely applied as the major treatment modality for the clinical intervention against bone fractures. However, the intrinsic bioinertness of Ti and its alloys often impedes the effective osseointegration of the implants, leading to severe adverse complications including implant loosening, detachment, and secondary bone damage. Consequently, new Ti implant engineering strategies are urgently needed to improve their osseointegration after implantation. Remarkably, metalorganic frameworks (MOFs) are a class of novel synthetic material consisting of coordinated metal species and organic ligands, which have demonstrated a plethora of favorable properties for modulating the interfacial properties of Ti implants. This review comprehensively summarizes the recent progress in the development of MOF-coated Ti implants and highlights their potential utility for modulating the bio-implant interface to improve implant osseointegration, of which the discussions are outlined according to their physical traits, chemical composition, and drug delivery capacity. A perspective is also provided in this review regarding the current limitations and future opportunities of MOF-coated Ti implants for orthopedic applications. The insights in this review may facilitate the rational design of more advanced Ti implants with enhanced therapeutic performance and safety. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are peculiar multimodal materials that find photocatalytic applications for the decomposition of lethal molecules present in the wastewater. In this investigation, two new d10-configuration-based MOFs, [Zn2(L)(H2O)(bbi)] (1) and [Cd2(L)(bbi)] (2) (5,5-(1,4-phenylenebis(methyleneoxy)diisophthalic acid (H2L) and 1,1′-(1,4-butanediyl)bis(imidazole) (bbi)), have been synthesized and characterized. The MOF 1 displayed a (4,6)-connected (3.43.52)(32.44.52.66.7) network topology, while 2 had a (3,10)-connected network with a Schläfli symbol of (410.511.622.72)(43)2. These MOFs have been employed as photocatalysts to photodegrade nitrophenolic compounds, especially p-nitrophenol (PNP). The photocatalysis studies reveal that 1 displayed relatively better photocatalytic performance than 2. Further, the photocatalytic efficacy of 1 has been assessed by altering the initial PNP concentration and photocatalyst dosage, which suggest that at 80 ppm PNP concentration and at its 50 mg concentration the MOF 1 can photo-decompose around 90.01% of PNP in 50 min. Further, radical scavenging experiments reveal that holes present over 1 and ·OH radicals collectively catalyze the photodecomposition of PNP. In addition, utilizing density of states (DOS) calculations and Hirshfeld surface analyses, a plausible photocatalysis mechanism for nitrophenol degradation has been postulated. [ABSTRACT FROM AUTHOR]

Four new metal–organic frameworks based on cobalt(II) salts and 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide (odabco) were obtained. Their crystallographic formulae are [Co3(odabco)2(OAc)6] (1, OAc− = acetate), [Co(H2O)2(HCOO)2]·odabco (2), [Co2(H2O)(NO3)(odabco)5](NO3)3·3.65H2O (3), and [Co2(DMF)2(odabco)4](NO3)4·3H2O (4; DMF = N,N-dimethylformamide). Crystal structures of 1–4 were determined by single-crystal X-ray crystallography. Coordination polymer 1 comprises binuclear and mononuclear metal–acetate blocks alternating within uncharged one-dimensional chains, in which odabco acts as a bridging ligand. A layered Co(II) formate 2 contains odabco only as guest molecules located in the interlayer space. Layered compound 3 and three-dimensional 4 have cationic coordination frameworks with 26% and 34% specific void volumes, respectively, unveiling high structural diversity of Co(II)-odabco MOFs based on quite a rare aliphatic moiety. Magnetization measurements were performed for 1, 3, and 4 and the obtained data were interpreted on the basis of their crystal structures. A strong (J/kB~100 K) antiferromagnetic coupling was found within binuclear metal blocks in 1. Ion exchange experiments revealed a considerable iodide uptake by 3 resulting in an up to 75% guest nitrate substitution within the voids of a coordination framework, found by capillary zone electrophoresis data and confirmed by single-crystal XRD. A preservation of 3 crystallinity during the exchange allowed for the guest I− positions within a new adduct with the formula [Co2(H2O)(NO3)(odabco)5]I2(NO3)·1.85H2O (3-I) to be successfully determined and the odabco aliphatic core to be revealed as a main adsorption center for quite large and easily polarizable iodide anions. In summary, this work presents a comprehensive study for a series of 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide-based MOFs of cobalt(II) within the framework of magnetic properties and reports the first example of anion exchange in odabco-based coordination networks, supported by direct X-ray structural data. The reported results unveil promising applications of such frameworks bearing ligands with an aliphatic core in the diverse structural design of selective adsorbents and other types of functional materials. [ABSTRACT FROM AUTHOR]

The selection of metal centers can endow donor–metal–accepter (D–M–A) type MOFs with progressive framework dimensions. 3D Cd-based MOFs with intramolecular charge transfer caused by D–M–A exhibit a satisfactory photothermal conversion efficiency of 35.7%, with the temperature rapidly rising from 25 °C to 201 °C in 7 s under 808 nm laser irradiation. [ABSTRACT FROM AUTHOR]

This paper illustrates how the size and type of substituent R in the phosphinate group of ferrocenyl bisphosphinic acids can affect conformational possibilities and coordination packing. It also demonstrates that H-phosphinate plays a key role in variational mobility, while Me- or Ph- substituents of the phosphinate group can only lead to 0D complexes or 1D coordination polymer. Overall, this paper provides valuable insights into the design and construction of coordination polymers based on ferrocene-contained linkers. It sheds light on how different reaction conditions and substituents can affect conformational possibilities and coordination packing, which could have significant implications for developing new polymers with unique properties. [ABSTRACT FROM AUTHOR]

Electrocatalytic reduction of CO2 to valuable chemicals can alleviate the energy crisis, and solve the greenhouse effect. The key is to develop non-noble metal electrocatalysts with high activity, selectivity, and stability. Herein, bimetallic metal organic frameworks (MOFs) materials (BiZn-MOF, BiSn-MOF, and BiIn-MOF) were constructed by coordinating the metals Zn, In, Sn, and Bi with the organic ligand 3-amino-1H-1,2,4-triazole-5-carboxylic acid (H2atzc) through a rapid microwave synthesis approach. The coordination centers in bimetallic MOF catalyst were regulated to optimize the catalytic performance for electrochemical CO2 reduction reaction (CO2RR). The optimized catalyst BiZn-MOF exhibited higher catalytic activity than those of Bi-MOF, BiSn-MOF, and BiIn-MOF. BiZn-MOF exhibited a higher selectivity for formate production with a Faradic efficiency (FE = 92%) at a potential of −0.9 V (vs. RHE, reversible hydrogen electrode) with a current density of 13 mA cm−2. The current density maintained continuous electrolysis for 13 h. The electrochemical conversion of CO2 to formate mainly follows the *OCHO pathway. The good catalytic performance of BiZn-MOF may be attributed to the Bi-Zn bimetallic coordination centers in the MOF, which can reduce the binding energies of the reaction intermediates by tuning the electronic structure and atomic arrangement. This study provides a feasible strategy for performance optimization of bismuth-based catalysts. [ABSTRACT FROM AUTHOR]

Precise control of the structure and spatial distance of Lewis acid (LA) and Lewis base (LB) sites in a porous system to construct efficient solid frustrated Lewis pair (FLP) catalyst is vital for industrial application but remains challenging. Herein, we constructed FLP sites in a polyoxometalate (POM)‐based metal–organic framework (MOF) by introducing coordination‐defect metal nodes (LA) and surface‐basic POM with abundant oxygen (LB). The well‐defined and unique spatial conformation of the defective POM‐based MOF ensure that the distance between LA and LB is at ~4.3 Å, a suitable distance to activate H2. This FLP catalyst can heterolytically dissociate H2 into active Hδ−, thus exhibiting high activity in hydrogenation, which is 55 and 2.7 times as high as that of defect‐free POM‐based MOF and defective MOF without POM, respectively. This work provides a new avenue toward precise design multi‐site catalyst to achieve specific activation of target substrate for synergistic catalysis. [ABSTRACT FROM AUTHOR]