Enhanced water stability of MOFs multiple hydrogen bonds and their application in water harvesting.

A mechanism based on multiple hydrogen bonds was proposed to describe the great water stability of some hydrated Cu paddle-wheel-based MOFs, which was demonstrated through density functional theory (DFT) calculations and single-crystal X-ray diffraction (SCXRD) of water-loaded MOFs. This mechanism endowed Cu-TDPAT with exceptional water stability and outstanding atmospheric water harvesting capability.

Photodimerization-Triggered Photopolymerization of Triene Coordination Polymers Enables Macroscopic Photomechanical Movements.

Controlling the packing of olefinic molecules in crystals is essential for triggering solid-state [2 + 2] photocycloaddition reactions and the synthesis of photocontrolled smart materials. Herein, we report the stepwise photodimerization-triggered photopolymerization of two triene coordination polymers (CPs), {[Zn(2-BBA)(tpeb)]·0.5CHCN} (, 2-HBBA = 2-bromobenzoic acid, tpeb = 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene) and {[Zn(3-BBA)(tpeb)]·CHCN)} (, 3-HBBA = 3-bromobenzoic acid).

Tandem Protocol for Diversified Deuteration of Secondary Aliphatic Amines under Mild Conditions.

Deuteration of amine compounds has been widely of concern because of its practical role in organic reaction mechanisms and drug research; however, only limited deuteration label methods are accessible with DO as a deuterium source. Herein, we propose a convenient deuteration protocol, including preparing D by the AlGa activation method, using PtRu nanowires as catalysts, and utilizing the elementary step in the couple reaction involving an imine unit, to realize the rapid preparation of a secondary amine with a diversified deuteration label. The self-coupling between nitriles not only provides a symmetric secondary amine with four α-D atoms but also produces high-valued ND in an atomic-economic way.

In Situ Fe/Co/B Codoped MoS Ultrathin Nanosheets Enable Efficient Electrocatalytic Nitrogen Reduction.

The development of sustainable and effective electrochemical nitrogen fixation catalysts is crucial for the mitigation of the terrible energy consumption resulting from the Haber-Bosch process. Molybdenum disulfide (MoS) exhibits promise toward nitrogen reduction reaction (NRR) on account of its similar structure to natural nitrogenases MoFe-co but still undergoes serious challenges with unsatisfactory catalytic performance resulted from limited active sites, conductivity, and selectivity. In this work, Fe/Co/B codoped MoS ultrathin nanosheets are synthesized and verified as excellent NRR catalysts with high activity, selectivity, and durability.

Liquid Gallium-Assisted Pyrolysis of MOF Affording CNT Non-Hollow Frameworks in High Yields for High-Performance Sodium-Ion Battery Anode.

Carbon materials have great potential for applications in energy, biology, and environment due to their excellent chemical and physical properties. Their preparation by carbonization methods encounters limitations and the carbon loss during pyrolysis in the form of gaseous molecules results in low yield of carbon materials. Herein a low-energy (600 °C) and high-yield (82 wt.

Zwitterionic Thiolate-Protected Ag(0/I) and Ag(I) Clusters: Assembly, Structural Characterization, and Antibacterial Activity.

Zwitterionic thiolate ligands have the potential to introduce novel assembly modes and functions for noble metal clusters. However, their utilization in the synthesis of silver clusters remains understudied, particularly for the clusters containing reductive Ag(0) species. In this article, we report the first synthesis of a mixed-valence silver(0/I) cluster protected by zwitterionic Tab as thiolate ligands (Tab = 4-(trimethylammonio)benzenethiolate), denoted as [Ag(Tab)](PF)·16CHOH·6EtO (·16CHOH·6EtO), alongside an Ag(I) cluster [Ag(Tab)(PhCOO)(MeCN)(HO)](PF)·11MeCN (·11MeCN).

The Use of Photocycloaddition Reactions to Drive Mechanical Motions Resembling Humanoid Movements.

With the aim of producing a photomechanical material for incorporation in soft microrobots, a one-dimensional diene coordination polymer (CP) [Cd(F-bpeb)(3-CBA)] (CP1, F-bpeb=4,4'-((1E,1'E)-(2,5-difluoro-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine, 3-HCBA=3-chlorobenzoic acid) was synthesized and characterized. Irradiation of CP1 with ultraviolet (UV) or visible light causes [2+2] photocycloaddition reactions resulting in the introduction of crystal strain which triggers various types of crystal movements. Composite films of CP1-PVA (SC) fabricated by dispersing CP1 crystals into polyvinyl alcohol (PVA) solution allow amplification of the crystal movement so that the film strips exhibit fast and flexible curling upon photoirradiation.

Polyhedral {Ag} and {Ag} Clusters: Synthesis, Structural Characterization and Third-Order Nonlinear Optical Properties.

Two polyhedral silver-thiolate clusters, [S@Ag(Tab)(MeCN)](PF) (Ag) and [Ag(Tab)(DMF)](PF) (Ag), were synthesized by using electroneutral Tab species as protective ligands (Tab=4-(trimethylammonio)benzenethiolate, DMF=N,N-dimethylformamide, MeCN=acetonitrile). Ag has a decahedral shape composed of eight pentagon {Ag} units and two square {Ag} units. The structure of Ag is a cuboctahedron, a classical Archimedean structure composed of six triangular faces and eight square faces.

Interfacial Electronic Interactions Between Ultrathin NiFe-MOF Nanosheets and Ir Nanoparticles Heterojunctions Leading to Efficient Overall Water Splitting.

Creating specific noble metal/metal-organic framework (MOF) heterojunction nanostructures represents an effective strategy to promote water electrolysis but remains rather challenging. Herein, a heterojunction electrocatalyst is developed by growing Ir nanoparticles on ultrathin NiFe-MOF nanosheets supported by nickel foam (NF) via a readily accessible solvothermal approach and subsequent redox strategy. Because of the electronic interactions between Ir nanoparticles and NiFe-MOF nanosheets, the optimized Ir@NiFe-MOF/NF catalyst exhibits exceptional bifunctional performance for the hydrogen evolution reaction (HER) (η = 15 mV, η denotes the overpotential) and oxygen evolution reaction (OER) (η = 213 mV) in 1.

Construction of olefinic coordination polymer single crystal platforms: precise organic synthesis, exploration of reaction mechanisms and beyond.

Olefin [2+2] photocycloaddition reactions based on coordination-bond templates provide numerous advantages for the selective synthesis of cyclobutane compounds. This review outlines the recent advances in the design and construction of single crystal platforms of olefinic coordination polymers for precise organic synthesis, exploration of reaction mechanisms, and possible developments as comprehensively as possible. Numerous examples are presented to illustrate how the arrangements of the olefin pairs influence the solid-state photoreactivity and examine the types of cyclobutane products.

Thermal evaporation-driven fabrication of Ru/RuO nanoparticles onto nickel foam for efficient overall water splitting.

Developing high-performance bifunctional electrocatalysts towards the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) holds great significance for efficient water splitting. This work presents a two-stage metal-organic thermal evaporation strategy for the fabrication of Ru-based catalysts (Ru/NF) through growing ruthenium (Ru)/ruthenium dioxide (RuO) nanoparticles (NPs) on nickel foam (NF). The optimal Ru/NF shows remarkable performance in both the HER (26.

In situ observation of a stepwise [2 + 2] photocycloaddition process using fluorescence spectroscopy.

Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms. However, investigating the early stages of solid-state reactions/transformations is still challenging. Here we introduce in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer platform.

Regulation of Crystal Structures and Solid-State Photoreactivity of Diolefin Coordination Polymers by Carboxylate Ligands.

Olefinic coordination polymers (CPs) have recently drawn more attention, owing to the many possibilities in conformational conversions and photochemical reactivity that olefin molecules offer. In the presence of different carboxylic acids, we utilize one diolefin ligand 4,4'-((1E,1'E)-(2,5-dimethoxyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine (OCH-bpeb) and Cd(II) to assemble six different crystalline CPs (-). By fine-tuning the substituent size, carboxyl group number, and geometrical configuration of carboxylate ligands, these diolefin CPs show quite different crystal architecture models, from one-dimensional intersecting stacking to one-dimensional parallel stacking to three-dimensional interpenetrated structure.

Self-Assembly of Cluster-Mediated 3D Catenanes with Size-Specific Recognition Behavior.

Although interlocked three-dimensional molecules display unique properties associated with their spatial structures, their synthesis and study of their host-guest properties remain challenging. We report the formation of a novel [2]catenane, [EtN]@[(Tp*WSCuCl)(-bpype)](OTf) ([EtN][](OTf)), by self-assembly of the cluster node [Tp*WSCuCl] and the organic linker ()-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)phenyl)ethene (-bpype). Single-crystal X-ray and NMR analyses established that [] is formed by the interpenetration of two cluster-organic cages.

Screening of transition metal and boron atoms co-doped graphdiyne catalysts for electrocatalytic urea synthesis.

Electrocatalytic CN coupling using nitrogen (N) and carbon dioxide (CO) as precursors offers a promising alternative for urea production under mild conditions, compared to traditional synthesis approaches. However, the design and screening of extremely efficient electrocatalysts remains a significant challenge in this field. Hence, we propose a systematic approach to screen efficient double-atom catalysts (DACs) with both metal and boron active sites, employing density functional theory (DFT).

Reversible Single-Crystal-to-Single-Crystal Transformations between Nanoscale 2D Nanosheets and 3D Metal-Organic Frameworks.

Single-crystal-to-single-crystal (SCSC) transformations provide more possibilities for phase transitions, which have attracted great attention in crystal engineering. In this paper, we report a series of reversible SCSC transformations between nanoscale two-dimensional layered double hydroxide (LDH) crystals and three-dimensional metal-organic framework crystals. They can proceed not only in solution systems but also on the surface of solid-state polyacrylonitrile films and fibers.

Introducing Frustrated Lewis Pairs to Metal-Organic Framework for Selective Hydrogenation of -Heterocycles.

Hydrogenated nitrogen heterocyclic compounds play a critical role in the pharmaceutical, polymer, and agrochemical industries. Recent studies on partial hydrogenation of nitrogen heterocyclic compounds have focused on costly and toxic precious metal catalysts. As an important class of main-group catalysts, frustrated Lewis pairs (FLPs) have been widely applied in catalytic hydrogenation reactions.

Visible Light and Microwave-Mediated Rapid Trapping and Release of Singlet Oxygen Using a Coordination Polymer.

Due to its high reactivity and oxidative strength, singlet oxygen ( O ) is used in a variety of fields including organic synthesis, biomedicine, photodynamic therapy and materials science. Despite its importance, the controlled trapping and release of O is extremely challenging. Herein, we describe a one-dimensional coordination polymer, CP1, which upon irradiation with visible light, transforms O (triplet oxygen) to O .

Phase Transition-Promoted Rapid Photomechanical Motions of Single Crystals of a Triene Coordination Polymer.

Molecular crystals with the ability to transform light energy into macroscopic mechanical motions are a promising class of materials with potential applications in actuating and photonic devices. In regard to such materials, coordination polymers that exhibit dynamic photomechanical motion, associated with a phase transition, are unknown. Herein, we report an intriguing photoactive, one-dimensional Zn coordination polymer, 1, derived from 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene and 3,5-difluorobenzoate.

Design of a MOF-based nano-trap for the efficient separation of propane from propylene.

A parallel Cu paddle wheel structure was developed to form an efficient CH nano-trap. Benefiting from having this trap, ATC-Cu showed a very high capacity for binding CH and high CH/CH selectivity at 298 K.

CoSe nanoparticles anchored on dual 1D carbon nanotubes/N-doped carbon nanofibers as high-performance anodes for sodium-ion storage.

Transition metal chalcogenides (TMCs) have been widely explored and utilized in sodium-ion battery (SIB) anodes owing to their unique advantages, such as high theoretical specific capacity and low cost. However, their inherent defects, such as low electronic conductivity and severe volume expansion, seriously limit the further development of TMC-based anodes. Here, a novel composite material of CoSe nanoparticles (NPs) encapsulated in a dual one-dimensional (1D) carbon composite structure (CoSe@CNTs/N-CNFs) was designed deliberately.

Photopolymerization-Driven Macroscopic Mechanical Motions of a Composite Film Containing a Vinyl Coordination Polymer.

We report a unique vinyl coordination polymer (CP), [Zn(4-Fb) (tkpvb)] (1, 4-HFb=4-fluorobenzoic acid, tkpvb=1,2,4,5-tetrakis(4-pyridylvinyl)benzene) that undergoes a rare photopolymerization reaction to form a two-dimensional CP integrated with a one-dimensional linear organic polymer. Upon light irradiation at different wavelengths, 1 exhibits an unprecedented phenomenon of photoinduced nonlinear lattice expansion. 1 can be uniformly dispersed in polyvinyl alcohol (PVA) to form the composite film of 1-PVA.

Coordination Polymer-Mediated Molecular Surgery for Precise Interconversion of Dicyclobutane Compounds.

A Cd(II)-based coordination polymer {[Cd(5-F-1,3-bpeb)(FBA)]·HO} () was obtained from Cd(II) salt, 5-fluoro-1,3-bis[2-(4-pyridyl)ethenyl]benzene (5-F-1,3-bpeb), and -fluorobenzoic acid (HFBA). Within the one-dimensional chain structure of , a pair of 5-F-1,3-bpeb was arranged in a face-to-face style. Upon UV irradiation and heat treatment, multiple cyclobutane isomers, including specific monocyclobutanes ( with an -cyclobutane ring in and with an -cyclobutane ring in ) and dicyclobutanes (,-dicyclobutane in , ,-dicyclobutane in , and ,-dicyclobutane in ) were stereoselectively produced.

Regulation of the Coordination Structures of Transition Metals on Nitrogen-Doped Carbon Nanotubes for Electrochemical CO Reduction.

The electrochemical carbon dioxide reduction reaction (CORR) has been extensively studied due to its potential to reduce the globally accelerating CO emission and produce value-added chemicals and fuels. Despite great efforts to optimize the catalyst activity and selectivity, the development of robust design criteria for screening the catalysts and understanding the role of water and potassium for CO activation poses a significant challenge. Herein, a rapid method for screening single-atom catalysts (SACs) possessing different coordination structures toward the CORR process to form CO, namely, a metal atom supported on nitrogen-doped carbon nanotubes (M@CNT, M@1N_CNT, M@2N_CNT, and M@3N_CNT), was established using large-scale density functional theory computations.