Revealing the effect of electrolyte coordination structures on the intercalation chemistry of batteries

In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking the Al/graphite battery as a model system,the effect of electrolyte coordination structure on the intercalation processes has been investigated over the batteries with either 1-hexyl-3-methylimidazolium chloride(HMICl)-AlCl_(3) or 1-ethyl-3-methylimidazolium chloride(EMICl)-AlCl_(3) ionic liquid electrolyte using operando X-ray photoelectron spectroscopy(XPS)and X-ray diffraction.With a weaker anion-cation interaction in HMI-based electrolyte,the XPS-derived atomic ratio between cointercalated N and intercalated Al is 0.9,which is lower than 1.6 for EMI-based electrolyte.Attributed to the additional de-solvation process,the batteries with the HMI-based electrolyte show a lower ionic diffusion rate,capacity,and cycling performance,which agree with the operando characterization results.Our findings highlight the critical role of the electrolyte coordination structure on the(co-)intercalation chemistry.

Relationship between Coordination Structure and Biological Activity of Copper(II) Nicotinate

The copper（Ⅱ） complexes of pyridine-3-carboxylic acid （nicotinic acid） and pyridine-2-carboxylic acid （isonicotinic acid） were synthesized, and their structures were characterized by elemental analysis, infrared spectrum, powder X-ray diffraction and so on. The results show that under experimental conditions, the ligands of synthesized copper nicotinate and copper isonicotinate are coordinated simultaneity with copper（Ⅱ） via the nitrogen of pyridine group and an oxygen of carboxylic acid group to form bidentate chelates. The crystal of copper nicotinate with two six-membered chelate rings belongs to monoclinic system, while that of copper isonicotinate having two five-membered chelate rings is of triclinic system. The tests show that the biological activities, such as the improvement of feed utilization, growth, anti-oxidation ability of organism and disease-resistant power, are different when copper nicotinate, copper inicotinate, copper-lysine chelate, copper-methionine chelate and copper sulphate are added in pig＇s feed, respectively. Due to its higher biological activity, less pollution and lower toxicity, copper nicotinate has wide potential applications as a feed additive.

A New Luminescent Cd(Ⅱ) Coordination Polymer Constructed by Mixed 1,4-Naphthalenedicarboxylate and N-donor Chelating Ligand

In this work, we synthesized a new two-dimensional Cd（Ⅱ） coordination polymer, [Cd（1,4-NDC）（L）]（1）, by using mixed 1,4-naphthalenedicarboxylic acid（1,4-H2NDC） and typical chelating N-donor ligands 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-f][1,10]phenanthroline ligand（L）. Compound 1 crystallizes in monoclinic, space group P21/n with a = 12.936（5）, b = 15.245（5）, c = 13.499（5） ？, β = 105.456（5）o, V = 2565.9（16） A^3, Z = 4, C（31）H（16）CdClFN4O4, Mr = 675.33, Dc = 1.748 g/cm^3, F（000） = 1344, μ（MoKa） = 1.011 mm^-1, R = 0.0350 and wR = 0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd（Ⅱ） atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N–H···O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.

A Three-dimensional Zn^(Ⅱ) Based Coordination Polymer with 2-Fold Interpenetrated Topology Displaying Luminescent Property

A new coordination polymer, [Zn2（m-bix）（p-bdc）2] （1）, was synthesized under hydrothermal conditions by a reaction of 1,3-bis（imidazol-l-ylmethyl）benzene （m-bix）, 1,3-benzene- dicarboxylic acid （H2p-bdc） and Zn（NO3）2. The colorless block crystals of complex 1 （C30H22N408Zn2） belong to the triclinic system, space group P1 with a = 10.213（2）, b = 12.052（2）, c = 12.392（3） A, a = 82.97（3）, β = 76.04（3）, y = 78.02（3）°, V= 1443.8（5） A3, Z = 2, Dc = 1.604 g/cm3, Mr = 697.26, F（000） = 708, R = 0.0403 and wR = 0.0907 for 4886 observed reflections （1 〉 2σ（I））. In 1, the tetrahedral Zn11 cations are linked by [p-bdc]2- anions into 2D sql networks, which are further connected by bix ligands forming an interesting 2-fold 4,4-connected mog-type 3D network with a point symbol of {4·6^4·8}^2{4^2·6^2·8^2}. Complex 1 was characterized by elemental, IR spectroscopy, powder X-ray diffractions and thermalgravimetric analysis. In addition, complex 1 exhibits coordination induced photoluminescent property.

Synthesis,Structure and Photoluminescence of a New Pb(Ⅱ)Coordination Polymer[Pb(1,4-chdc)(L)]n·nH2O Based on a Flexible 1,4-Cyclohexanedicarboxylic Acid

A new Pb（Ⅱ） coordination polymer, [Pb（1,4-chdc）（L）]_n·nH_2O（1）, was synthesized under hydrothermal condition（1,4-H2 chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-（3-fluorophenyl）-1H-imidazo[4,5-f][1,10]phenanthroline）. Its crystal structure was determined by singlecrystal X-ray diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 9.1182（8）, b = 11.3249（10）, c = 12.7326（12） A, α = 77.897（2）, β = 81.644（2）, γ = 84.491（2）°, V = 1269.0（2） A^3, Z = 2, C_（27）H_（24）FN_4O_5Pb, M_r = 710.69, D_c = 1.860 g/cm^3, F（000） = 690, μ（MoKa） = 6.701 mm^（-1）, R = 0.0349 and wR = 0.0746. In 1, each 1,4-chdc anion bridges two neighboring Pb（Ⅱ） atoms in a bidentate chelating coordination mode to give a chain structure. The L ligands are attached on one side of the chain through chelating the Pb（Ⅱ） atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. The O-H···O and N-H···O hydrogen bonding interactions further stabilize the supramolecular layer structure of 1. Moreover, solid state luminescent property of 1 was also studied.

Ionothermal Synthesis, Crystal Structure and Photocatalytic Property of a New Cobalt Coordination Polymer

The reaction of flexible bis（imidazole） ligand and 1,2-bis（imidazol-l＇-yl）methane （bimm） with Co（Ⅱ） salt under ionothermal method resulted in the formation of a new coordination polymer {[Co（bimm）3]·（PF6）2}n （1）. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the triclinic Pi space group, with α = 8.647（6）, b = 12.092（9）, c = 14.967（1 l） A, α = 88.912（8）, β = 81.199（8）, ）, = 89.395（8）°, V= 1546 （2） A3, Z = 2, Mr = 793.39, Dc= 1.704 Mg/m3,μ = 0.768 mm-1 F（000） = 798, the final R = 0.0626 and wR = 0.1634 for 4319 observed reflections with I〉 2σ（I）. In compound 1, the Co（lI） ion is connected to another Co（ll） by two bimm ligands to form 1D double chains which are further linked by bimm ligands to form a 2D wavelike layer. Topologically, the structure of 1 represents a uninodal 2D 4-connected sq1/Shubnikov tetragonal plane net. Moreover, thermogravimetric analyses and photocatalytic property for 1 have also been investigated.

Helical Coordination Polymer with a 3-Fold Interpenetration Structure Based on 5-(Hydroxymethyl)isophthalic Acid

5-（Hydroxymethyl） isophthalic acid （H2HIA） as a novel organic ligand was prepared from 3,5-bis（methoxycarbonyl）benzoic acid by a two-step method. And then, a 3D helical coor- dination polymer with a 3-fold interpenetration structure, namely [Zn1/2（HIA）1/2（DPEE）1/2]n （1）, was hydrothermally synthesized at 160 ℃, using H2HIA ligands to assemble with DPEE ligands and Zn2＋ ions. Complex 1 crystalizes in orthorhombic system, space group Pnna, with a = 8.2118（5）, b = 17.1698（7）, c =14.9922（7） ？, V = 2113.82（18） ？3, μ = 1.194 mm-1, Z = 4 and S = 0.967. Moreover, some physical characteristics of complex 1, such as powder X-ray diffraction （PXRD）, thermogravimetry analyses （TGA） and photoluminescent properties, were also investigated.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain-like coordination polymer [Mn（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized from 2,4,6-trimethylbenzoic acid, 1,10-phenanthroline and anhydrous manganese（Ⅱ ） sulfate and then characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.05643（16）, b = 2.05643（16）, c = 1.3939（2） nm, V = 5.8946（11） nm^3, Mr = 579.54, Z = 8, Dc = 1.306 g/cm^3, μ（MoKα） = 0.490 mm^-1, F（000） = 2424, S = 0.985, the final R = 0.0411 and wR = 0.0950. The Flack factor is -0.01（2）. The crystal structure shows that two neighboring man- ganese（Ⅱ ） ions are linked together by one bridge-chelating 2,4,6-trimethylbenzoic group, forming a one-dimensional chain structure. The manganese（Ⅱ ） ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline, three oxygen atoms from three 2,4,6-trimethylbenzoic acids and one water oxygen atom, giving a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex was also investigated.

A Chain Cadmium(Ⅱ) Coordination Polymer with Diacylhydrazide: Synthesis,Crystal Structure and Luminescent Property

A novel Cd（Ⅱ） coordination polymer with diacylhydrazide ligand N,N？-bis（3-methoxysalicyl）-2,6-pyridinedicarbohydrazide（H_6msphz）,[Cd_2（H_2msphz）（Py）_4]_n（1,Py = pyridine） has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230（11）,b = 11.7264（15）,c = 17.3395（14） ？,α = 70.520（9）,β = 84.806（7）,γ = 81.965（9）°,V = 2089.9（4） ？~3,Dc = 1.638 gcm^（–3）,μ = 1.083 mm^（-1）,F（000） = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd（Ⅱ） ion,but also its two terminal groups to chelate other two Cd（Ⅱ） ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π＊ transitions.

Crystal Structures and Photoluminescent Properties of Two Cd^(2＋) Coordination Polymers Constructed from an 8-Hydroxyquinolinate Ligand

In order to perform a study on the structural modulation in the Cd（Ⅱ）-L architecture（HL =（E）-2-[2-（3-pyridyl）ethenyl]-8-hydroxyquinoline）, two different dicarboxylic acids, namely, 2-aminoterephthalic acid（H_2ATA） and 4,4￠-biphenyldicarboxylic acid（H_2BPDC）, are employed as the secondary auxiliary ligands. Two new complexes [Cd_2L_2（ATA）]（1） and [Cd_2L_2（BPDC）·2MeO H· 4H_2O]（2） with distinct 3D frameworks were obtained. In complex 1, ligands ATA bridge the 1D Cd（Ⅱ）-L infinite chains into a 3D polymeric coordination network. Complex 2 is a 3D porous framework, in which adjacent 2D Cd（Ⅱ）-L coordination layers were linked together by the coor- dinated BPDC ligands. The variant structures of two complexes indicate that the skeleton of dicarboxylate anions plays a great role in the assembly of such different frameworks. In addition, the photoluminescent properties（fluorescent emission, lifetime, and quantum yield） of polymers 1 and 2 were also investigated in the solid state.

Two Cobalt(Ⅱ)Coordination Polymers Based on Tetrazylphosphonate and Tetrazylphosphonic Acid Ligands

Two cobalt coordination polymers with the same 2D structure have been hydrothermally synthesized based on two bifunctional ligands with tetrazole and phosphonate（phosphonic acid） groups,namely,diethyl 4-（2H-1,2,3,4-tetrazol-5-yl） benzylphosphonate（C_2H_5-L1） and 4-（2H-1,2,3,4-tetrazol-5-yl）benzylphosphonic acid（H_2L2）. The structures of the two complexes are characterized by elemental analysis,IR,TGA and X-ray single-crystal/powder diffraction. The pink block crystals of complex [Co（L1）（H_2O）]·H_2O（1） belong to the monoclinic system,space group C2/m with a = 20.8390（11）,b = 7.2695（3）,c = 10.0156（6） A,β = 109.773（7）°,V = 1427.80（13） A^3,Z = 4,D_c = 1.680 mg/cm^-3,M_r = 361.16,F（000） = 740,R = 0.0316 and wR = 0.0826 for 1702 observed reflections（I 〉 2σ（I））. The purple block crystals of complex [Co（L2）（H_2O）]·2H_2O（2） also belong to the monoclinic system,space group C2/c with a = 25.5382（16）,b = 7.3844（3）,c = 15.1925（11） A,β = 124.238（9）°,V = 2368.6（2） A^3,Z = 8,D_c = 1.969 mg/cm^-3,M_r = 351.12,F（000） = 1432,R = 0.0475,wR = 0.1617 for 2088 observed reflections（I 〉 2σ（I））. Both the nitrogen atoms of tetrazole group and oxygen atoms of phosphonate（phosphonic acid） groups in the ligands coordinated with the metal cobalt. The magnetic property of complex 1 is also investigated.

Synthesis,Crystal Structure and Photoluminescent Property of a Novel Dy^(3+) Coordination Compound Containing Rare(H_2O)_(22) Clusters

A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.

STUDY ON THE STRUCTURES OF COORDINATION COMPOUNDS OF N-(ortho-METHYL)-AND N-(ortho-METHOXY)-PHENYL IMINODIACETATO-Cu(Ⅱ)

The coordination compounds,{Cu[CH_3C_6H_4N(CH_2COO)_2]}.2H_2O and {Cu[CH_3OC_6H_4N(CH_2COO)_2]}.2H_2O,have been prepared and its crystal struc- tures determined.The final discrepancy factors are R=0.052,R_w=0.061 for (I)and R=0.052,R_w=0.039 for(Ⅱ).The geometry of the coordination poly- hedron with Cu(Ⅱ)is a distorted tetragonal pyramid for(Ⅰ)and an unsym- metrical and extended tetragonal bipyramid for(Ⅱ),respectively.The re- sults of EHMO calculations indicate that the ligand mainly provided the field with very few of its electrons being coordinated to the central atom.

Solvothermal Synthesis,Crystal Structure and Photoluminescence Property of a 3D Lead(Ⅱ)Coordination Polymer Based on Terephthalic Acid

Solvothermal reaction of Pb（NO3）2·6H2O with rigid linear ligand terephthalic acid（H2pta） in N,N-dimethylformamide（DMF） produced a new three-dimensional（3D） lead（Ⅱ）coordination polymer[Pb2（pta）1.5（μ4-OH）（DMF）]n 1,and its structure was characterized by single-crystal X-ray diffraction analyses.In polymer 1,the μ4-OH bridges the nearby lead（Ⅱ） ions into an infinite one-dimensional（1D） chain,and then the organic ligand pta^2- joins the neighbored chains into a 3D structure by two similar connection modes in different configurations.The solid-state photoluminescent studies revealed that 1 exhibits a strong greenish emission mainly originating from ligand-to-metal charge transfer between the delocalized π bonds of the aromatic carboxylate ligand pta^2- and the p orbitals of the Pb^2＋ centers.

Coordination Structure of Aluminum in Magnesium Aluminum Hydroxide Studied by (27)Al NMR

The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV increased with the increase of the ratio of Al/Mg and with the peptizing temperature. AlIV originated from the so-called Al13 polymer with the structure of one Al tetrahedron surrounded by twelve Al octahedrons.

Synthesis and Characterization of a Novel Coordination Complex Based on Fluorescein

A novel coordination complex,{[Cd）2（C（20）H（10）O5）2（H2O）4]·10H2O}n,has been synthesized based on fluorescein（2-（6-hydroxy-3-oxo-3 H-xanthen-9-yl） benzoic acid） and systematically characterized by elemental analysis,infrared（IR） spectrum,thermo gravimetric analysis（TGA）,powder X-ray diffraction（PXRD） and single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic,space group P2/n with a = 20.428（5）,b = 8.084（2）,c = 21.689（5）A,β = 96.360（5）°,Mr = 993.46,V = 3559.7（15）A^3,Z = 4,Dx = 1.845 g/cm^3,μ = 1.276 mm^-1,F（000） = 1974,GOOF = 1.044,λ（Mo Kα） = 0.71073 ？,the final R = 0.0553 and wR = 0.1720 for 7245 observed reflections with I 〉 2σ（I）.

Syntheses and Structures of a New Tetrazylphosphonate Ligand and the Coordination Polymer Based on Zn^(Ⅱ)

A novel tetrazylphosphonate ligand, namely ethyl 4-（2-ethyl-2H-1,2,3,4-tetrazol-5-yl） benzylphosphonate（Et-L）, was designed and successfully achieved from p-cyano benzyl chloride, based on which a zinc coordination polymer（1） with a 2D layer structure has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The colorless block crystals of H_2L·H_2O were also obtained under the same hydrothermal conditions, which belongs to monoclinic system, space group P2_1/c with a = 13.3141（7）, b = 5.1650（3）, c = 21.9839（18） A, β = 115.307（5）°, V = 1366.69（15）A3, Z = 4, D_c = 1.391 mg/cm^（-3）, Mr = 349.58, F（000） = 600, R = 0.0748 and wR = 0.1917 for 2392 observed reflections（I 〉 2σ（I））. The colorless block crystals of complex 1（[Zn（L）（H_2O）]_n） also belong to monoclinic system, space group P2_1/c with a = 22.7464（10）, b = 6.0430（3）, c = 9.7704（4） ？, β = 92.525（4）°, V = 1341.70（10）A3, Z = 4, D_c = 1.731 mg/cm_（-3）, M_r = 349.58, F（000） = 712, R = 0.0596 and wR = 0.1688 for 2357 observed reflections（I 〉 2σ（I））. Only the oxygen atoms of phosphonic group are coordinated with the metal zinc probably because the hydrogen atom of tetrazole has been substituted by ethyl group. Photoluminescence properties of the complex are also investigated.

STUDY ON SYNTHESIS,CHARACTERIZATION AND STRUCTURE OF A NEW RARE EARTH COORDINATION COMPOUND WITH BENZOIC ACID

In this paper,a new rare earth benzoate coordination compound,[TbL_3(HL)(H_2O)]_2 (HL=C_7H_6O_2=benzoic acid) is synthesized and characterized by elemental analysis DTA,TG,DTC,and IR spectra.The title compound crystallizes in triclinic,space.group P with a=9.148(1),b=11.460(2), c=13.506(2);α=112.76(1),β=91.83(1),γ=91.99(1)°;Z=1;V=1303.3.The final R factor is 0.0235.The rare earth ion is nine-coordinated to form a distorted monocapped square antiprism.

A Cd(Ⅱ)Coordination Polymer with cds Topology Constructed by Polycarboxylate and Imidazole-containing Ligand

A new Cd（Ⅱ） coordination polymer,{[Cd（pda）（bimb）]·（H2O）（0.5）}n（1,H2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis（1-imidazolyl）biphenyl）,has been synthesized and characterized by elemental analysis,IR spectroscopy,powder X-ray diffraction（PXRD） analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpenetrated three-dimensional（3-D） cds topology. In additional,photoluminescent properties of 1 and its dehydrated product have also been studied.

Construction and the Second-order Nonlinear Optics of a New Chiral Coordination Network Based on Two Types of Homo-chiral Helices

A new 2D chiral cadmium coordination network [Cd（TCBA）2]？2EtOH （1） was prepared by the reaction of achiral angular asymmetric bridging ligand 2-（（3,5-dimethyl- 4H-1,2,4-triazol-4-yl）-carbamoyl）-benzoic acid （TCBA） with cadmium acetate, which was structurally characterized by IR, elemental analysis, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 crystallizes in the chiral space group P21 and features a 2D chiral network consisting of two types of homo-chiral helices, which are further extended into a 3D chiral framework along the a-axis via hydrogen bonds. Moreover, powder second-order nonlinear optical （NLO） measurements reveal complex 1 has a modest second-harmonic-generation （SHG） efficiency at room temperature.