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Dual 1D CoSe2@CNTs/N-CNFs obtained by electrospinning and subsequent two-step heating process exhibit superior sodium-ion storage performance when used as the anode of an SIB.

An MOF with an optimized C3H6 nano-trap exhibited a high capacity to bind C3H6 and high C3H6/C3H8 selectivity at 298 K.

A Cd(II)-based coordination polymer {[Cd

Overcoming thermal quenching is an essential issue in the practical application of luminescent materials. Herein, we found that negative thermal expansion (NTE) can achieve the thermal enhancement of luminescence in molecular materials based on three metal-organic frameworks CuX-bpy (X = Cl, Br, I; bpy = 4,4'-bipyridine). All complexes exhibit NTE on the

Four coordination polymers with similar 1D chain motifs exhibited different photosalient behaviors, which can be tuned via monomer preorganization.

One Zn(ii) coordination polymer is used to selectively detect CrO42− and Fe3+ in water via luminescence quenching and enhancement methods.

Solvothermal reactions of cadmium salts with bipyridyl diene and triene ligands[(1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene-(1,3-bpeb) and 1,6-bis(4-pyridyl)-1,3,5-hexatriene(bphte)] and one bipyridyl triene ligand[1,6-bis(4-pyridyl)-1,3,5-hexatriene-(bphte)] in the presence of auxiliary carboxylic acids including 2,6-dichlorobenzoic acid(2,6-HDCBA) and 2-naphthal-enecarboxylic acid(2-HNCA) gave rise to four coordination polymers [Cd(bphte)(2,6-DCBA)2]n(1), {[Cd(bphte)(2-NCA)2]·5.8H2O}n(2), [Cd2(1,3-bpeb)2(2,6-DCBA)4]n(3) and {[Cd4(1,3-bpeb)4(2-NCA)7(HCOO)]·2-HNCA·H2O}n(4), respectively. Compounds 1–4 were structurally characterized by elemental analysis, IR, 1H NMR, powder X-ray diffraction, thermogravimetric analysis and single-crystal X-ray diffraction. They possess one-dimensional linear(1, 2) and zigzag(3, 4) chain structures. Their luminescent properties were explored while the representative sample 4 exhibited good luminescent performance in sensing Fe(III) in water.

Sodium-ion batteries (SIBs) have aroused great attention because of the low cost and environmental benignity of sodium resources. However, practical applications of SIBs are plagued by the sluggish kinetics of sodium ions with large size in the host structure, which results in poor rate performance and rapid capacity decline. Herein, a self-templated approach was developed to synthesize MoS2 /Cu2 Se nanosheets with improved interfacial electron- and ion-transfer kinetics. The MoS2 /Cu2 Se nanosheets provided superior sodium storage performance, delivering 139 mAh g-1 at a high current density of 100 A g-1 and 222 mAh g-1 after 14000 cycles (at 20 A g-1 ). The outstanding electrochemical performance was attributed to the synergetic engineering of interface and structure, which could enhance the electrochemical kinetics and gave excellent mechanical properties to deal with the volume expansion phenomenon. Combined with a high-voltage cathode, the full battery demonstrated a high energy density of 152 Wh kg-1 at a power density of 420 W kg-1 , which opens a new avenue for the development of high-performance SIBs.

Reactions of (NH4 )2 WS4 with CuCN, CuCN/1,2-bis(4-pyridyl)propane (bppa) or [Cu(MeCN)4 ]PF6 /bppa under different reaction conditions afforded a set of two- or three-dimensional W/Cu/S cluster-based coordination polymers including {[Et4 N]2 [WS4 Cu4 (μ-CN)2 (μ-I)2 ]}n (1), [WS4 Cu4 (μ-CN)2 (bppa)2 ]n (2) and {[WS4 Cu4 (bppa)4 ](PF6 )2 }n (3), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two-dimensional networks with a "sql" topology, while 3 possesses a two-fold interpenetrated three-dimensional net with a rare "reo" topology. Compounds 1-3 in DMF exhibited different third-order nonlinear optical responses, and they all showed a reverse saturable absorption while 2 held a strong self-focusing effect.

An exceptional Zn-based MOF material with two-fold hetero-interpenetrated nets consisting of a 3D lcy network and a novel 3D (3,9)-coordinated framework has been constructed. The Zn-based MOF exhibits a rare yellow-green fluorescence and can be used as a fluorescence sensor to detect carbaryl with a detection limit of 4.5 μM.

Using simple methods to obtain efficient catalysts has been a long-standing goal for researchers. In this work, the employment of a one-pot pyrolysis reaction to achieve molecular confinement, has led to the preparation of ruthenium (Ru)-based nanoclusters in a carbon matrix. A unique feature of the synthetic approach employed is that solvent and substrates were calcined together. As solvent evaporates, during calcination, the substrates form a dense solid which has the effect of limiting the aggregation of Ru centers during the carbonization process. The catalyst prepared in this simple manner showed an impressively high activity with respect to the hydrogen/oxygen evolution reaction (HER/OER). The Ru nanoclusters (Ru NCs), as the hydrogen evolution reaction (HER) catalysts, require ultralow overpotentials of 5 mV and 5.1 mV at −10 mA·cm−2 in 1.0 M KOH, and 0.5 M H2SO4, respectively. Furthermore, the catalyst prepared by the one-pot method has higher crystallinity, a higher Ru content and an ultrafine cluster size, which contributes to its exceptional electrochemical performance. Meanwhile, the RuOX nanoclusters (RuOX NCs), obtained by oxidizing the aforementioned Ru NCs, exhibited good oxygen evolution reaction (OER) performance with an overpotential of 266 mV at 10 mA·cm−2. When applied to overall water splitting, Ru/RuOX nanoclusters as the cathode and anode catalysts can reach 10 mA·cm−2 at cell voltages of only 1.49 V in 1 M KOH.

Two atom-precise silver nanoclusters [Ag25Cl2(Tab)14(PhCOO)11(DMF)4](PF6)12 (Ag25, DMF=N,N-dimethylformamide) and [Ag26Cl2(Tab)14(PhCOO)13(DMAc)4](PF6)11(Ag26, DMAc=N,N-dimethylacetamide) were synthesized based on the electrically neutral thiolate protective ligand, 4-(trimethylammonio)benzenethiolate (Tab). The weak Ag-S interaction in Tab-protected silver nanoclusters allows to insert or leave a single silver atom in the Ag-S skeleton through solvent-trigger core fragmentation and re-arrangement, thereby realizing the reversible conversion of Ag25 and Ag26 for the first time.

Controlling the morphology of highly homogeneous nanoribbons is one of the main goals for synthesizing catalysts with excellent activity and durability. In this Communication, platinum (Pt) nanoribbons were synthesized by a one-pot method. We used ammonium fluoride (NH4F) as the regulator, under 8 atm of hydrogen (H2), to synthesize zigzag-shaped two-dimensional Pt nanoribbons. Benefiting from their unique morphology, the Pt nanoribbons display superior electrocatalytic activity and stability.

The treatment of the metal sulfide precursor [Et4N][Tp*WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with Cu(I) and the Fe-bipyridine complex ligand L1 in the presence of (NH4)2SO4 produced one-dimensional (1D) [(Tp*WS3Cu2)2(L1)2](BF4)2 (2) and two-dimensional (2D) [(Tp*WS3Cu3)2(L1)3(μ3-SO4)2] (3) heterometallic coordination polymers (CPs). Both CPs were characterized using elemental analysis, IR spectra, UV-vis spectra, mass spectra and single crystal X-ray diffraction. Compound 2 contains a butterfly-shaped core [Tp*WS3Cu2] serving as a two-connecting node to link its equivalent ones viaL1 bridges to form a 1D zigzag chain extending along the c axis. Compound 3 consists of a 2D layer structure with a (6,3) network in which each complete cubane-like core [Tp*WS3Cu3(μ3-SO4)] works as a pyramidal three-connecting node to link its equivalent ones viaL1 bridges. The formation of the different structural topologies of 2 and 3 may be ascribed to the different precursor-to-Cu(I) molar ratios (1 : 2 for 2 and 1 : 3 for 3). The cluster modular construction (CMC) was used to simplify the structural modules of 2 and 3 as straightforward modules to clarify the possible process of assembly and structural characteristics. In addition, the third-order nonlinear optical (NLO) properties of 2 and 3 in MeCN were investigated. They both displayed enhanced third-order NLO responses relative to those of 1 and L1.

Developing the highly efficient and low-cost electrocatalysts for the oxygen evolution reactions (OERs), as vital half reactions of water splitting, is crucial for renewable energy technology. The electrocatalysts based on multi-component and hierarchically structured non-noble metal hydr(oxy)oxide materials are of great prospects. Herein, we report an efficient strategy at low temperatures for synthesizing amorphous iron-doped cobalt-molybdenum ultrathin hydroxide (Fe-CoMo UH) nanosheets. Benefiting from the ultrathin amorphous structure and multi-metal coordination, Fe-CoMo UH nanosheets exhibit outstanding performance for OERs with a low overpotential of 245 mV at 10 mA cm−2, a small Tafel slope of 37 mV dec−1 and an excellent stability for 90 h. The mass activity of Fe-CoMo UH is higher than that of commercial Ir/C and most of the transition metal hydroxide catalysts. This work provides a feasible consideration for the construction of promising efficient non-noble metal catalysts.

A set of W/Cu/S cluster-supported supramolecular wire and rectangle compounds were assembled and exhibited enhanced third-order nonlinear optical responses.

Metal-organic framework (MOF) nanosheets with attractive chemical and structural properties have been considered as prominent oxygen evolution reaction (OER) electrocatalysts, while the insufficient exposed active sites and low electrical conductivity of MOFs limit their electrocatalytic activity and further industrial applications. Herein, a unique strategy to remarkably boost electrocatalytic OER activity of one Ni-based MOF is developed by the simultaneous incorporation of Fe

Stereoselective [2 + 2] photocycloaddition provides a desirable synthetic route for target cyclobutane compounds yet remains challenging. In this issue of Chem Catalysis, Weiss and coworkers diligently apply CdSe quantum dots to photocycloaddition reactions and gain nearly quantitative yields of syn-aryl-conjugated vinylcyclobutanes.

Discovering and constructing novel and fancy structures is the goal of many supramolecular chemists. In this work, we propose an assembly strategy based on the synergistic effect of coordination and covalent interactions to construct a set of octahedral supramolecular cages and adjust their degree of distortion. Our strategy innovatively utilizes the addition of sulfur atoms of a metal sulfide synthon, [Et4N][Tp*WS3] (A), to an alkynyl group of a pyridine-containing linker, resulting in a novel vertex with low symmetry, and of Cu(I) ions. By adjusting the length of the linker and the position of the reactive alkynyl group, the control of the deformation degree of the octahedral cages can be realized. These supramolecular cages exhibit enhanced third-order nonlinear optical (NLO) responses. The results offer a powerful strategy to construct novel distorted cage structures as well as control the degree of distortion of supramolecular geometries.

An efficient method for visible-light-initiated, nickel-catalyzed Sonogashira C(sp)–C(sp2) coupling has been developed via an energy-transfer mode. Thioxanthen-9-one as a photosensitizer could sign...

Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE- , single electron transfer (SET) in donor-acceptor complex (DAC) from *HE- to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE. to sulfone by the DAC method.

Hydrogen will be an important energy vector of the future, and improved efficiency in electrohydrolysis will accelerate this transition. In a fundamental study, we have prepared Co(II) and Ni(II) complexes of a new PNN type ligand N-((diphenylphosphanyl)methyl)-2-amino-1,10-phenanthroline (dppmaphen) incorporating the photoactive 1,10-phenanthroline group and the strongly coordinating diphenylphosphine to obtain photoelectrochemical (PEC) catalysts [Co(dppmaphen)2(NO3)2] (1) and [Ni(dppmaphen)2Cl]Cl (2) which catalyzed the hydrogen evolution reaction (HER) in alkaline media (1 M KOH). Overpotentials (η10) of 430 (1) and 364 mV (2) could be reduced to 345 (1) and 284 mV (2) under Xe light irradiation. This irradiation generated photocurrent responses of 528 (1) and 357 uA/cm2 (2). Density function theory (DFT) calculation on the frontier orbitals of 1 and 2 were useful in understanding these differences in catalytic performance.

Metallic sulfides have emerged as highly active, durable, and robust electrocatalysts for the electrocatalytic hydrogen evolution reaction (HER) due to their intriguing electronic and catalytic properties. One of the important strategies to further enhance their HER performance is to build multimetallic nanostructures by tuning the electronic state. Here we combine multimetallic structures and metal sulfides, and report an efficient strategy for the in situ surface-derivation of molybdenum sulfide nanosheets (MoS2 NSs) on Ag–Pd–Mo alloy nanowires (AgPdMo NWs) to form AgPdMo/MoS2 NWs. The heterostructure incorporates AgPdMo NWs with high conductivity and MoS2 NSs with abundant active sites, which act synergistically in alkaline solution. The as-tuned AgPdMo/MoS2 NWs exhibit Pt-like electrocatalytic performance for the HER, with a small overpotential of 54 mV at a current density of 10 mA cm−2 and a low Tafel slope of 72 mV dec−1. The present work demonstrates a potential strategy for designing heterostructures with multimetallic composition by in situ surface-derivation with enhanced performance in water splitting.

A conjugated nanoporous polycarbazole (CNP) cross-linked by pyridine and coordinated to Co(III) displays high catalytic performance for visible light-driven H2 generation. The hydrogen evolution rate was up to 410 μmol g−1 h−1. Spectroscopic and electrochemistry studies indicate that the redox active cobalt reduces recombination of photoexcited-charge-carriers and enhances the transmission of photoexcited-charge, thereby enriching the catalytic activity of hybrid materials x-Co/CNP-N (x = 5, 10, 15 and 20 wt%).

To obtain a pure product without the isomer byproducts is a goal that many chemists are pursuing. As one kind of very important synthesis method, the photochemical reaction is simple and straightforward yet low-selective. In this work, a coordination interaction-based oriented synthesis strategy has been proposed to realize the precise stereochemical control of the isomeric cyclic compounds in the photocycloaddition reaction. Through fixing the reactants via coordination interactions, the arrangements and configurations of the reactants can be adjusted, thereby successfully producing all of the related photocycloaddition products without isomer byproducts for the first time. This work not only provides a new route to synthesize the pure cyclic compounds but also expands the application of the photocycloaddition reaction.

Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.

Sodium-ion batteries (SIBs) have aroused great attention because of the low cost and environmental benignity of sodium resources. However, practical applications of SIBs are plagued by the sluggish kinetics of sodium ions with large size in the host structure, which results in poor rate performance and rapid capacity decline. Herein, a self-templated approach was developed to synthesize MoS

This review summarizes the syntheses, crystal structures and applications of metal complexes with a specific zwitterionic thiolate ligand, 4-(trimethylammonio)benzenethiolate (Tab). The chemistry of Tab with transition metals (Fe, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, Hg), main group metals (In, Pb, Bi) and in heterometallic systems is described. The most significant structural features of the metal/Tab complexes are summarized and trends are discussed as a function of nuclearity and coordination numbers. The reactivity of specific metal/Tab complexes towards N- and P- donor ligands, organic acids, inorganic anions and metal ions is discussed. The luminescence and dielectric properties of the metal/Tab complexes and their applications as fluorescent biosensors and precursors to metal nanoparticles and catalysts for organic transformations are also illustrated.

Design and synthesis of non-noble metal electrocatalysts with high activity and durability for the electrolysis of water is of great significance for energy conversion and storage. In this work, we prepared a series of Fe-doped MoS2 nanomaterials by simple one-pot solvothermal reactions of (NH4)2MoS4 with FeCl3·6H2O. An optimized working electrode of Fe-MoS2-5 displayed high hydrogen evolution reaction (HER) activity with a relatively small overpotential of 173 mV to achieve a current density of 10 mA cm-2 in 0.5 M H2SO4, along with no significant change in catalytic performance even after 1000 cyclic voltammetry (CV) cycles. Fe-MoS2 nanoparticles on nickel foam (NF; denoted as Fe-MoS2/NF) exhibited an overpotential of 230 mV at 20 mA cm-2 for the oxygen evolution reaction (OER) and 153 mV at 10 mA cm-2 for the HER in 1.0 M KOH electrolyte. Fe-MoS2/NF was stable for more than 140 h under these conditions. Furthermore, the two electrode system of Fe-MoS2/NF (anode)//Fe-MoS2/NF (cathode) electrodes demonstrated excellent electrocatalytic activity toward overall water splitting with a low potential of 1.52 V at 10 mA cm-2 in 1.0 M KOH electrolyte.