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A zinc supracluster [Zn24(ATZ)18(AcO)30(H2O)1.5]·(H2O)3.5 (Zn24), and a 1D zinc supracluster chain {[Zn24(ATZ)18(AcO)30(C2H5OH)2(H2O)3]·(H2O)2.5}n (1-D⊂Zn24) with molecular diameters of 2 nm were synthesized under regulatory solvothermal conditions or the micro bottle method. In an N,N-dimethylformamide solution of Zn24, Fe3+, Ni2+, Cu2+, Cr2+ and Co2+ ions exhibited fluorescence-quenching effects, while the rare earth ions Ce3+, Dy3+, Er3+, Eu3+, Gd3+, Ho3+, La3+, Nd3+, Sm3+, and Tb3+showed no obvious fluorescence quenching. In ethanol solution, the Zn24 supracluster can be used to selectively detect Ce3+ ions with excellent efficiency (limit of detection (LOD) = 8.51 × 10−7 mol/L). The Zn24 supracluster can also detect wavelengths between 302 and 332 nm using the intensity of the emitted light. [ABSTRACT FROM AUTHOR]

The electronic state in terms of charge and spin of metal sites is fundamental to govern the catalytic activity of a photocatalyst. Herein, we show that modulation of the electronic states of Cu sites, without changing the coordination environments, of two metal‐organic supramolecular assemblies based on π⋅⋅⋅π stacking can significantly improve photocatalytic activity. The use of these heterogeneous photocatalysts, without using noble metal cocatalysts, resulted in an increase of the hydrogen production rate from 522 to 3620 μmol h−1 g−1. A systematical analysis revealed that the charge density and spin density of the metal centers are efficiently modulated via the modulation of the coordination fields around active copper (II) centers by the variation of the non‐coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight into the electronic state of active metal centers for designing high‐performance photocatalysts. [ABSTRACT FROM AUTHOR]

Metal‐complex‐based materials for lithium storage have attracted great interest due to their highly designable structures with multiple active sites and well‐defined lithium transport pathways. Their cycling and rate performances, however, are still constrained by structural stability and electrical conductivity. Herein, we present two hydrogen‐bonded complex‐based frameworks with excellent lithium storage capability. Multiple hydrogen bonds among the mononuclear molecules result in three‐dimensional frameworks that are stable in electrolyte. The origin of the remarkable lithium storage performance of this family was revealed through kinetic analysis and DFT calculations. [ABSTRACT FROM AUTHOR]

Entacapone (ENT) is a powerful catechol‐O‐methyl transferase inhibitor that is used for the diagnosis and treatment of Parkinson's syndrome, but the amount used must be well controlled to avoid overtreatment and side effect. Fast and selective detection of ENT needs well‐matched energy levels and well‐designed sensor‐ENT interaction which is highly challenging. In this work, a water stable europium‐based metal‐organic framework (Eu‐TDA) was synthesized to detect ENT by luminescence with excellent reusability and selectivity in the presence of main coexisting and interference species of plasma with a limit of detection of 5.01 μM. The experimental results showed that the luminescence of Eu‐TDA can be effectively quenched by ENT via well‐designed photoinduced electron transfer mechanism and internal filtration effect mechanism in the system. [ABSTRACT FROM AUTHOR]

Cadmium‐based coordination polymers, namely, {[Cd(HL)(L)] ⋅ HN(Et)3}n (1), [Cd2(L)2(H2O)5]n (2), [Cd(L)(phen)]n (3), [Cd(L)(2,2′‐bpy)]n (4), [Cd(L)(4,4′‐bpy)]n (5), [Cd(L)(bpp)]n (6), [Cd(L)(dpa)]n (7), {[Cd(L)(dpa)] ⋅ H2O}n (8) (H2L=4,4′‐((p‐tolylazanediyl)bis(methylene))dibenzoic acid, phen=1,10‐phenanthroline, 2,2′‐bpy=2,2′‐bipyridine, 4,4′‐bpy=4,4′‐bipyridine, bpp=1,3‐bis(4‐pyridyl)propane, dpa=bis(4‐pyridyl)amine) have been synthesized in hydro/solvothermal reactions. 1 is a 4‐connect 3D network with an eightfold interpenetrating diamond topology. The 1D ladder chain structure of 2 was composed of the dinuclear [Cd2(CO2)4] subunit bridged with two L2− ligands. 3 shows a 1D double‐chain with a channel formed by edging out the coordination water with the rigid co‐ligand phen. Polymer 4 displays a 2D lamellar structure based on superseding the coordination water molecules by the rigid chelating auxiliary ligands 2,2′‐bpy. By substituting the small molecules with a rigid bridging ligand 4,4′‐bpy, a 2D undulating structure of 5 was built. Compounds 6 and 7 exhibit a 2D layer structure with a 4‐connect (44 ⋅ 62) sql‐net. Compound 8 presents a 3D architecture with a sixfold interpenetrating diamond topology. Through our construction strategy, versatile structures from 1D–3D have been rationally designed by controlling the process condition and rigid/flexible of N‐donor spacers. Additionally, the photoluminescence, charge transfer, and electrochemical luminescence (ECL) properties of 1–8 have been demonstrated. Flexible and versatile: A flexible 4,4′‐((p‐tolylazanediyl)bis(methylene))dibenzoic acid ligand (H2L) was used to assemble Cd2+ ions and produce a series of eight coordination polymers. The polymer structures range from 1D to 3D, and can be rationally designed by controlling the reaction conditions and rigidity/flexibility of the N‐donor spacers. Moreover, the photoluminescence, charge transfer, and electrochemical luminescence (ECL) properties of the complexes are influenced by their conformation. [ABSTRACT FROM AUTHOR]

Front Cover: Hydrogen-bonded Complex-based Frameworks for Stable Lithium Storage (Chem. Lithium-ion battery, Metal-organic complex, Hydrogen-bonded framework, Dimensional design Keywords: Lithium-ion battery; Metal-organic complex; Hydrogen-bonded framework; Dimensional design EN Lithium-ion battery Metal-organic complex Hydrogen-bonded framework Dimensional design 1 1 1 07/05/23 20230703 NES 230703 B Hydrogen-bonded complex-based frameworks b were applied for the development of high-performance anode materials of lithium-ion batteries. [Extracted from the article]

Abstract: A new penta‐nuclear Fe(III) cluster, [Fe5(μ3‐O)2L3(HL)(ATZ)4]⋅4H2O (1), (H2L is 2‐(((1H‐tetrazol‐5‐yl)imino)methyl)phenol, HATZ is 5‐Amino‐1H‐tetrazole) was synthesized through micro‐vial method. Complex 1 was characterized by elemental analysis, fourier transform infrared (FTIR), X‐ray single crystal diffraction, powder X‐ray diffraction (Powder XRD) and thermogravimetric analysis. Moreover, the magnetic properties and Hirshfeld surface analysis of 1 were investigated and discussed in detail. [ABSTRACT FROM AUTHOR]

Four novel linear trinuclear manganese clusters [Mn 3 (L n ) 2 (CH 3 COO) 4 ] ( 1 , n = 1; 2 , n = 2; 3 , n = 3; 4 , n = 4. where HL 1 is 4-chloro-2-((2-(6-chloropyridin-2-yl)hydrazono)methyl)phenol, HL 2 is 4-bromo-2-((2-(6-chloropyridin-2-yl)hydrazono)methyl)phenol, HL 3 is 4-chloro-2-((2-(6-bromopyridin-2-yl)hydrazono)methyl)phenol, HL 4 is 4-bromo-2-((2-(6-bromopyridin-2-yl) hydrazono)methyl)phenol) were synthesized through solvothermal method. Complexes 1 – 4 were characterized by IR, and X-ray single-crystal diffraction. Complexes 1 – 4 are isomorphous compounds which are trinuclear linear manganese clusters. A detailed analysis of Hirshfeld surface and 2D fingerprint plots revealed that 1 – 4 were supported mainly by H⋯H, H⋯X (X = Cl, Br) and O⋯H intermolecular interactions. Magnetic properties of 1 – 4 have been studied. In additional, complex 3 showed highly intense electrochemicaluminescence (ECL) in DMF solution. [ABSTRACT FROM AUTHOR]

The local charge distribution of photocatalyst is crucial to the catalytic activity due to its influence on the charge separation process. Herein, we report two one-dimensional Ni-based metal-organic assemblies for efficient photocatalytic hydrogen evolution without using noble-metal cocatalysts. By adjusting the aromatic ring in the center of the tricarboxylic ligand, the photocatalytic hydrogen evolution activity was increased from 1715 to 2652 μmol h-1 g-1. The detailed mechanism study shows that the introduced nitrogen atoms in the ligands of the metal-organic coordination assembly could modulate the local charge distribution, and yielding a significant enhancement of the molecular dipole moment which engenders a propulsive force for the effective separation and transport of photoinduced charge carriers. This work provides insights into the local charge distribution via ligand modulation for enhancing the activity of photocatalysts., (© 2024 Wiley‐VCH GmbH.)

The electronic state in terms of charge and spin of metal sites is fundamental to govern the catalytic activity of a photocatalyst. Herein, we show that modulation of the electronic states of Cu sites, without changing the coordination environments, of two metal-organic supramolecular assemblies based on π⋅⋅⋅π stacking can significantly improve photocatalytic activity. The use of these heterogeneous photocatalysts, without using noble metal cocatalysts, resulted in an increase of the hydrogen production rate from 522 to 3620 μmol h -1  g -1 . A systematical analysis revealed that the charge density and spin density of the metal centers are efficiently modulated via the modulation of the coordination fields around active copper (II) centers by the variation of the non-coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight into the electronic state of active metal centers for designing high-performance photocatalysts., (© 2023 Wiley-VCH GmbH.)

Metal-complex-based materials for lithium storage have attracted great interest due to their highly designable structures with multiple active sites and well-defined lithium transport pathways. Their cycling and rate performances, however, are still constrained by structural stability and electrical conductivity. Herein, we present two hydrogen-bonded complex-based frameworks with excellent lithium storage capability. Multiple hydrogen bonds among the mononuclear molecules result in three-dimensional frameworks that are stable in electrolyte. The origin of the remarkable lithium storage performance of this family was revealed through kinetic analysis and DFT calculations., (© 2023 Wiley-VCH GmbH.)

Fast and selective Li + transport in solid plays a key role for the development of high-performance solid-state electrolytes (SSEs) of lithium metal batteries. Porous compounds with tunable Li + transport pathways are promising SSEs, but the comprehensive performances in terms of Li + transport kinetics, electrochemical stability window, and interfacial compatibility are difficult to be achieved simultaneously. Herein, we report a porous coordination chain-based hydrogen-bonded framework (NKU-1000) containing arrayed electronegative sites for Li + transport, exhibiting a superior Li + conductivity of 1.13 × 10 -3 S cm -1 , a high Li + transfer number of 0.87, and a wide electrochemical window of 5.0 V. The assembled solid-state battery with NKU-1000-based SSE shows a high discharge capacity with 94.4% retention after 500 cycles and can work over a wide temperature range without formation of lithium dendrites, which derives from the linear hopping sites that promote a uniformly high-rate Li + flux and the flexible structure that can buffer the structural variation during Li + transport.

Persistent organic pollutants (POPs) exist widely in the environment and place significant impact on human health by bioaccumulation. Efficient recognition of POPs and their removal are highly challenging tasks because their specific structures interact often very weakly with the capture materials. Herein, a molecular nanocage ( 1 ) is studied as an efficient sensing and sorbent material for POPs, which is demonstrated by a representative and stable perfluorooctane sulfonate (PFOS) substrate containing a hydrophilic sulfonic group and a hydrophobic fluoroalkyl chain. A highly sensitive and unusual turn-on fluorescence response within 10 s and a 97% total removal of PFOS from water in 20 min have been achieved owing to the strong host-guest interactions between 1 and PFOS. The binding constant of 1 to PFOS is 2 orders of magnitude higher than state-of-the-art adsorbents for PFOS and thus represents a new benchmark material for the recognition and removal of PFOS. The host-guest interaction has been elucidated by solid-state NMR spectroscopy and single-crystal X-ray diffraction, which provide key insights at a molecular level for the design of new advanced sensing/sorbent materials for POPs.

Entacapone (ENT) is a powerful catechol-O-methyl transferase inhibitor that is used for the diagnosis and treatment of Parkinson's syndrome, but the amount used must be well controlled to avoid overtreatment and side effect. Fast and selective detection of ENT needs well-matched energy levels and well-designed sensor-ENT interaction which is highly challenging. In this work, a water stable europium-based metal-organic framework (Eu-TDA) was synthesized to detect ENT by luminescence with excellent reusability and selectivity in the presence of main coexisting and interference species of plasma with a limit of detection of 5.01 μM. The experimental results showed that the luminescence of Eu-TDA can be effectively quenched by ENT via well-designed photoinduced electron transfer mechanism and internal filtration effect mechanism in the system., (© 2021 Wiley-VCH GmbH.)

2-Aminoacetophenone ( 2-AA ) is a metabolite produced in large quantities by the pathogenic bacteria Pseudomonas aeruginosa (PA), which is a biomarker for PA in water. State-of-the-art analytical techniques to detect PA usually require expensive instruments and a long analysis time which are not suitable for real-time water quality monitoring, especially for high-quality drinking water. Herein, we reported the application of a europium metal-organic framework (Eu-MOF) as a luminescent sensing material, which provides a facile, environmentally friendly and low-cost way for the fast detection of PA in water. Eu-MOF shows a high sensitivity toward 2-AA with a K SV value of 3.563 × 10 4 M -1 , rapid luminescence response in 12 s and high-selectivity and anti-interference ability with the existence of common detection indexes in drinking water owing to the good match of the energy levels of Eu-MOF and 2-AA . A systematical optimization of the sensing conditions to enhance the sensing function of Eu-MOF for 2-AA was discussed in detail, to give fundamentals for the rational design of MOF-based sensing materials.

Benzophenone (BP) is an ultraviolet filter (UVF) widely used in personal care products such as sunscreens and cosmetics. Excessive exposure to BP-type UVFs is a potential threat to human's health because of their endocrine-disrupting activity. Water stability of lanthanide compounds is crucial when they serve as luminescent sensors because of the practicality and recyclability. In this study, a water-stable luminescent Zn-Tb heterometallic coordination polymer was rationally designed and synthesized for rapid detection of BP. This material showed a high quenching effect, excellent selectivity, and fast response toward BP.