Auxiliary Ligands Mediated One- and Two-dimensional Cd(Ⅱ) Coordination Polymers Incorporating Methyl-3- hydroxy-5-carboxy-2-Thiophenecarboxylate Ligand

Two N-donor ligands mediated Cd（Ⅱ） coordination polymers, namely,[Cd（L）（dmpz）2]n （1） and {[Cd（L）（atr）05（H20）]（H2O）}n （2） （H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethylpyrazole, and atr= 4-amino-l,2,4-triazole）, havebeen produced. Their structures were characterized by single-crystal X-ray diffraction analysis,elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional （1D） chainstructure and is finally extended into a three-dimensional （3D） supramolecular architecturethough hydrogen bonding interactions. Compound 2 features a two-dimensional （2D） networkwith 4-connected sql topology based on dinuclear Cd（Ⅱ） clusters as nodes, which is alsoassembled into a 3D supramolecular architecture through hydrogen bonding interactions.Furthermore, compounds 1 and 2 exhibit high thermal stabilities and intense fluorescent emissionin the solid, and can be explored as potential luminescent materials.

Syntheses,Crystal Structures and Characterization of Two Coordination Polymers Based on Mixed Ligands

Two new coordination polymers,namely,{[Cd（1.5）（bc）2（HL）]（13）H2O}（2n）（1） and [Mn（ip）（H2L）（H2O）]n（2）（H2L = 3-（1 H-pyrazol-4-yl）-5-（pyridin-2-yl）-1,2,4-triazole,Hbc = benzoic acid,H2 ip = isophthalic acid） were constructed by solvothermal reaction.The compounds were characterized by elemental analysis,FT-IR spectroscopy,and single-crystal X-ray diffraction.Compound 1 displays a two-dimensional plane structure consisting of [Cd3（bc）2（HL）] subunits.Compound 2 possesses a one-dimensional chain structure and is further extended into a 3-D supramolecular architecture via hydrogen bonds.Moreover,photoluminescence studies showed compound 1 exhibits luminescent emissions with emission maxima at 375 nm.Magnetic susceptibility measurements of 2 indicate that domain antiferromagnetic interactions exist between Mn（Ⅱ） ions.In addition,thermogravimetric properties of 1 and 2 were also measured.

A(3,4)-Connected 3D Heteronuclear Framework with Three Kinds of Discrete Cadmium(Ⅱ) Ions: Synthesis,Crystal Structure and Luminescence Property

A novel 3D hetero-nuclear framework,namely [K_2Cd_5（Hbptc）_4（H_2O）_（12）·12H_2O]_n（1,H4 bptc = biphenyl-2,3,3？,5？-tetracarboxylic acid）,was obtained by hydrothermal reaction. X-ray singlecrystal structure analysis reveals that polymer 1 crystallizes in orthorhombic,space group Pbcn with a = 26.6152（13）,b = 11.7449（5）,c = 29.5923（14） ？,V = 9250.3（7） ？~3,C_（64）H_（76）Cd_5K_2O_（56）,Mr = 2381.44,Dc = 1.710 g/cm^3,μ（MoK α） = 1.323 mm^（-1）,F（000） = 4744,Z = 4,the final R = 0.0668 and wR = 0.1135 for 10613 observed reflections（I 〉 2σ（I））. Polymer 1 displays a 3D network that is built on the unprecedented heterobimetallic [Cd_3Cd_2K] molecular building block with a（3,4）-connected（6·8·8）2（6·6·82·82·126·126） topology which represents a rare 2-fold interpenetrating 3D framework topology network. The luminescence analyses reveal that polymer 1 shows obvious emission at room temperature in the solid state. In addition,it was also characterized by elemental,IR spectra and TG analyses.

Synthesis, Structure and Decarboxylative Behavior of a Nitro-coordinated Potassium Compound

A novel nitro-coordinated potassium compound [K(Htdc)(H_2O)]_n(tdc = 3-nitro-thiophene-2,5-dicarboxylate), has been synthesized and characterized. The complex with a two-dimensional(2D) layer structure contains an infinite K-O ladder-shaped chain, which is connected through carboxyl and unusual nitro-coordination of Htdc– anion. Then the 2D layers are further extended by intermolecular hydrogen-bonding to form a three-dimensional(3D) supramoleculalr network. Variable temperature powder X-ray diffractions, thermogravimetric analysis and nuclear magnetic resonance studies exhibit that the compound has a thermal-induced decarboxylative behavior.

Reactive ball-milling synthesis of Co-Fe bimetallic catalyst for efficient hydrogenation of carbon dioxide to value-added hydrocarbons

Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.

Aromatic Multicarboxylate Ligands Tuned One-and Three-dimensional Zn(Ⅱ) Coordination Polymers Based on 3-(1H-pyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole

Two aromatic multicarboxylate ligands tuned Zn(Ⅱ) coordination polymers, namely, {[Zn0.5(H2L)(tp)0.5(H2O)]H2O}n(1) and {[Zn2(HL)(btc)(H2O)]H2O}n(2)(H2L = 3-(1 Hpyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole, H2tp = terephthalic acid;H3 btc = 1,3,5-benzenetricarboxylic) have been synthesized. Their structures were characterized by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional chain structure and is finally extended into a three-dimensional supramolecular architecture though hydrogen bonding interactions. Compound 2 shows a three-dimensional framework. Meanwhile, compounds 1 and 2 exhibit luminescent emission in the solid, and can be investigated as potential luminescent materials.

Synthesis, Crystal Structure and Biothiols Detection Capability of a New “off-on” Fluoresent Probe

Biothiols such as cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)act as critical roles in maintaining biological redox homeostasis,which is crucial for a plenty of physiological and pathological processes.Therefore,the detection of biothiols is very important and beneficial for many applications.Herein,we have designed and developed a new crystal dimethyl 4-(2,4-dinitrophenylsulfonyloxy)pyridine-2,6-dicarboxylate(P)with 2,4-dinitrobenzene-1-sulfonyl(DNBS)pendant for light-up and detection of biothiols(Cys was selected as the analyte model).The fluorescence"off-on"switch is triggered by the cleavage of DNBS unit by the interaction with biothiols via nucleophilic aromatic substitution reaction.The turn-on fluorescent probe exhibited excellent selectivity and sensitivity toward biothiols.

Super high maximum on-state currents in 2D transistors

Two-dimensional(2D)materials have been recognized as a type of potential channel material to replace silicon in future field-effect transistors(FETs)by the International Technology Roadmap for Semiconductors(ITRS)and its succesor the International Roadmap for Devices and Systems(IRDS)[1−4].Substantial first principle quantum transport simulations have predicted that many 2D transistors,including those with MoS2,WSe2,phosphorene,and Bi2O2Se channels,own excellent device performance and are able to extend Moore’s law down to the sub-10 nm scale[4].

Structural Diversity and Luminescent Properties of Two Zinc(Ⅱ)Polymers Based on Semirigid N-heterocyclic Ligand

By varying the spacer angles of phenylenediacetic acid, two novel Zn（II） coordination polymers based on semirigid N-heterocyclic ligand 1,4-bis（2-ethylbenzimidazol-1-ylmethyl） benzene, [Zn（beb）0.5（m-phda）]n（1） and {[Zn（beb）（p-phda）]·2H2O}n（2）, were synthesized and fully structurally characterized. Polymer 1 exhibits a 2D grid-layer with a 44 topology. Polymer 2 shows a 2D layer with rare meso-helix. In addition, the thermal stability and photoluminescence properties of polymers 1 and 2 have also been investigated.

C-F insertion reaction sheds new light on the construction of fluorinated compounds

The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds,which have wide applications both in the academic and the industrial com-munities.The past three years have witnessed rapid developments in this field.This highlight provides an overview on the evolution according to the fluorinating agents used.

Size-controlled synthesis and near-infrared photothermal response of Cp^(*)Rh-based metalla[2]catenanes and rectangular metallamacrocycles

A variety of research reports on novel supramolecular topologies have been published over the last years.However,it is still a great challenge to tap into the inner functional properties of these complexes.Herein,two tetranuclear metallamacrocycles 1 and 2 and four octonuclear[2]catenanes 3-6 were constructed successfully via a coordination-driven self-assembly strategy,by conscious design and use of the tetramethyl bidentate pyridine ligand L1,and the appropriate selection of six binuclear half-sandwich rhodium building units with different longitudinal dimensions.The complexes have been fully characterized by single crystal X-ray diffraction analysis and NMR spectroscopy.Furthermore,near-infrared photothermal studies of the obtained[2]catenanes reveal different photothermal response in solid and solution states,which may be attributed to a strong fluorescence quenching effect of the half-sandwich organometallic fragment and different conjugated effect of Cp^(*)Rh based building blocks in the interlocking structures.The photothermal conversion efficiencies of[2]catenanes 4-6 fall in the range 30.5%-16.5% respectively.This contribution aims to play a key role in the experimental development of Cp^(*)-based photothermal materials.

Nuclei-rich galvanizing strategy for suppressing zinc dendrite growth

The uncontrolled growth of zinc dendrites on zinc anode hinders the application of zinc ion batteries.To solve this problem,Lu's group proposed a nuclei-rich galvanizing strategy for suppressing the zinc dendrite growth.This allows the nuclei-rich zinc electrode to cycle steadily for1200 h and have a high Coulombic efficiency of 99.7%at15 mA·cm^(-2)with a deposited amount of 10 mAh·cm^(-2).Moreover,the Zn-MnO_(2) battery with a low N/P ratio of 1.9exhibited sustained cycling life.

Zeolite polymer membrane as protective interface for Mg battery

Excessive electrolyte decomposition seriously determines the performance of high-voltage Mg batteries. In Nazar's work, the strategy using a zeolite polymer membrane as a protective interface was proposed to restrain the electrolyte decomposition. This strategy could boost Mg plating/stripping performance up to 6000 h in zeolite/Mg|zeolite/Mg symmetric cells and 91%capacity retention in zeolite/Mg||Mo_(3)S_(4)battery after 200 cycles.Energy storage devices have been intensively explored because of their important roles in our daily lives [1D3].

Iodized polyacrylonitrile as fast-charging anode for lithium-ion battery

In recent years,the fast-charging capability of the batteries is highly required,especially used for electric vehicles[1-4].Thus,the commercialized lithium-ion batteries(LIBs)which can be rapidly charged and stably cycled have a huge market prospect[5-7].However,the Li+transmission rate inside the electrode material/interface is sluggish in fast-charge condition,which usually leads to battery impedance increase,Li metal deposition,and electrolyte decomposition.

Ternary NiCoTi-layered double hydroxide nanosheets as a pH-responsive nanoagent for photodynamic/chemodynamic synergistic therapy

Combining photodynamic therapy(PDT)with chemodynamic therapy(CDT)has been proven to be a promising strategy to improve the treatment efficiency of cancer,because of the synergistic therapeutic effect arising between the two modalities.Herein,we report an inorganic nanoagent based on ternary NiCoTi-layered double hydroxide(NiCoTi-LDH)nanosheets to realize highly efficient photodynamic/chemodynamic synergistic therapy.The NiCoTi-LDH nanosheets exhibit oxygen vacancy-promoted electron-hole separation and photogenerated holeinduced O_(2)-independent reactive oxygen species(ROS)generation under acidic circumstances,realizing in situ pH-responsive PDT.Moreover,due to the effective conversion between Co^(3+)and Co^(2+)caused by photogenerated electrons,the NiCoTi-LDH nanosheets catalyze the release of hydroxyl radicals(-OH)from H_(2)O_(2)through Fenton reactions,resulting in CDT.Laser irradiation enhances the catalyzed ability of the NiCoTi-LDH nanosheets to promote the ROS generation,resulting in a better performance than TiO_(2)nanoparticles at pH 6.5.In vitro and in vivo experimental results show conclusively that NiCoTi-LDH nanosheets plus irradiation lead to efficient cell apoptosis and significant inhibition of tumor growth.This study reports a new pH-responsive inorganic nanoagent with oxygen vacancy-promoted photodynamic/chemodynamic synergistic performance,offering a potentially appealing clinical strategy for selective tumor elimination.

Synthesis of two lanthanide clusters Ln^(Ⅲ)_(4)(Gd_(4) and Dy_(4)) with [2×2] square grid shape:Magnetocaloric effect and slow magnetic relaxation behaviors

Two isostructural tetranuclear lanthanide clusters named [Ln_(4)(L)_(4)(CH_(3) O)_(4)]·CH_(3) OH(Ln=Gd(Ⅲ) for 1,Dy(Ⅲ) for 2,H_(2) L=N’-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide) were successfully isolated by using a polydentate Schiff based ligand and Ln(Ⅲ) nitrate salts.The structures of 1 and 2 were characterized by X-ray structural analyses,they are held by four double deprotonated ligands L2-.In them all the lanthanide ions are eight-coordinated and distributed over four vertices of a parallelogram,presenting a Ln4 cluster with a strict [2 × 2] square grid pattern.The details of magnetic analysis show that 1 displays weak anti-ferromagnetic exchange between neighboring Gd(Ⅲ) ions through carboxylate oxygen and methanol oxygen ligand atoms.Furthermore,1 exhibits significant magnetocaloric effect with the maximum entropy change-ΔSm value of 28.5 J/(kg K) for ΔH=7.0 T at 2.0 K.For compound 2,remarkable slow magnetic relaxation behaviors are observed in the presence of zero magnetic field with τ0=1.02 × 10^(-6) s and energy barrier ΔE/kB=43.24 K.

Frustrated Lewis Pairs:Discovery and Overviews in Catalysis

Frustrated Lewis Pairs(FLPs)are derived from simple combinations of Lewis acids(electron acceptors)and Lewis bases(electron donors),in which steric demands prevent from forming classical Lewis acid-base adducts.Since 2006,FLP chemistry has emerged as a novel strategy for the design and application of main-group chemistry and development of new metal-free catalytic processes.This strategy has been applied to stoichiometric reactivity and then extended to catalysis.In this review,we briefly summarize the representative discoveries and developments of FLP chemistry in the field of catalysis,including hydrogenation,hydrosilylation,reduction of C 02/transformations of alkynes to organic derivatives,C—H bond borylation and polymerization.

Two comparable Ba-MOFs with similar linkers for enhanced CO_(2)capture and separation by introducing N-rich groups

Two new different metal-organic frameworks(MOFs)[Ba(L1)(H_(2)O)_(2)]_(n)·nH_(2)O(MOF 1)and[Ba(L2)(-n2 O)_(2)]_(n)·0.5 nDMF·0.5 nH_(2)O(MOF 2)were yielded by the assembly of oxygen-friendly Ba(Ⅱ)ions and two similar linkers,namely 2-(imidazol-1-yl)terephthalic acid(H_(2)L1)and 2-(1 H-1,2,4-triazol-1-yl)terephthalic acid(H_(2)L2).Single-crystal X-ray diffractions(XRD)indicate that MOF1 is a new three-dimensional(3 D)stacking dense network formed by the one-dimensional(1 D)rod-shaped chains and L1 linkers,whereas MOF 2 presents a 3 D nanotube porous framework with cylindrical tunnels based on the 1 D loop chains as the secondary building units(SBUs)by replacing the imidazole group in H_(2)L1 with the triazole group in H_(2)L2.As a result,MOF 2 has a higher density of active sites and Lewis acid sites in the porous surface of nanotube than MOF 1.Thereby,the CO_(2)capture and separation capacity of MOF 2 is great higher than that of CH_(4)at298 K.

Effects of functional groups for CO_(2) capture using metal organic frameworks

Metal organic frameworks(MOFs)are promising adsorbents for CO_(2)capture.Functional groups on organic linkers of MOFs play important roles in improving the CO_(2) capture ability by enhancing the CO_(2) sorption affinity.In this work,the functionalization effects on CO_(2) adsorption were systematically investigated by rationally incorporating various functional groups including–SO3H,–COOH,–NH_(2),–OH,–CN,–CH_(3) and–F into a MOF-177 template using computational methods.Asymmetries of electron density on the functionalized linkers were intensified,introducing significant enhancements of the CO_(2) adsorption ability of the modified MOF-177.In addition,three kinds of molecular interactions between CO_(2) and functional groups were analyzed and summarized in this work.Especially,our results reveal that–SO_(3)H is the best-performing functional group for CO_(2) capture in MOFs,better than the widely used–NH_(2) or–F groups.The current study provides a novel route for future MOF modification toward CO_(2) capture.

Electrical contacts in monolayer blue phosphorene devices

Semiconducting monolayer （ML） blue phosphorene （BlueP） shares similar stability with ML black phosphorene （BP）, and it has recently been grown on an Au surface. Potential ML BlueP devices often require direct contact with metal to enable the injection of carriers. Using ab initio electronic structure calculations and quantum transport simulations, for the first time, we perform a systematic study of the interfacial properties of ML BlueP in contact with metals spanning a wide work function range in a field effect transistor （FET） configuration. ML BlueP has undergone metallization owing to strong interaction with five metals. There is a strong Fermi level pinning （FLP） in the ML BlueP FETs due to the metal-induced gap states （MIGS） with a pinning factor of 0.42. ML BlueP forms n-type Schottky contact with Sc, Ag, and Pt electrodes with electron Schottky barrier heights （SBHs） of 0.22, 0.22, and 0.80 eV, respectively, and p-type Schottky contact with Au and Pd electrodes with hole SBHs of 0.61 and 0.79 eV, respectively. The MIGS are eliminated by inserting graphene between ML BlueP and the metal electrode, accompanied by a transition from a strong FLP to a weak FLP. Our study not only provides insight into the ML BlueP-metal interfaces, but also helps in the design of ML BlueP devices.