Synthesis and Structure of a POMs-based 3D Zeolike Ionic Crystal,{[Co(dpdo)_2(H_2O)_2(CH_3CN)]_2(SiMo_(12)O_(40))(H_2O)_2}_n

A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.

Polyoxovanadate ionic crystals with open tunnels stabilized by macrocations for lithium-ion storage

Polyoxometalates(POMs)with multiple redox active sites have been reported as charge sponge for lithium-ion batteries(LIBs).Herein,we for the first time introduce a polyoxovanadate(POV)ionic crystals with macrocations,[Ni(Phen)_(3)][ClV_(14)O_(34)]Cl(NiV_(14),Phen=1,10-phenanthroline),as an anode material for LIBs.The existence of macrocation[Ni(Phen)_(3)]^(2+)stabilizes the open tunnels inside NiV_(14).The NiV_(14)electrode exhibits superior rate capabilities(1083 mAh·g^(-1)at 100 mA·g^(-1)and 384 mAh·g^(-1)at 2000 mA·g^(-1))due to the rapid capacitive dominated contribution and high Li^(+)ions diffusion coefficients(3.3×10^(-12) cm^(-2)·s^(-1)),and it delivers a remarkable cycling stability with a Coulombic efficiency of 99.7%after 1000 cycles at 2000 mA·g^(-1).Such performance can be attributed to the stable structure of NiV14 and the highly reversible valence changes of vanadium during the charge/discharge processes,which are revealed by a combination of in situ X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),and X-ray absorption fine structure(XAFS)measurements.This work not only demonstrates that NiV_(14) with open tunnels stabilized by macrocation is a promising anode material for high performance LIBs,but also provides important references for the rational design of POMs electrode materials in advanced energy storage systems.

Structure and ion transport properties of organic ionic compounds revealed by NMR

Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.

The Even-Odd and the Isoelectronicity Rules Applied to Single Covalent Bonds in Ionic, Double-Face-Centered Cubic and Diamond-Like Crystals

Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.

Lattice Energy Estimation for Complex Inorganic Ionic Crystal

A novel connectivity index ^mG based on adjacency matrix of molecular graphs was proposed as follows： ^mG = ∑（gi·gj·g…）^0.5. The element gi of adjacency matrix was defined as gi=（1＋Zi^1.4）/（1＋ri^1.4）, where Zi and ri are the charge number and the thermochemical radius of ion i respectively, and the radii ri for metal ions are taken to be the Goldschmidt radius. The regression analysis by the connectivity index 1G can provide a high-quality QSPR model for the lattice energies of 245 complex inorganic ionic crystal samples. The results imply, that the lattice energies may be expressed as a linear model of the connectivity index 1G. For the linear model the correlation coefficient r and the standard error s are 0.9998 and 228.72 kJ/mol, respectively. The cross-validation by the leave-one-out method demonstrates that the model is highly reliable from the point of view of statistics.

Ultrasonic generation via direct interaction between photons and phonons in anharmonic lattice of ionic crystals

A theory of ultrasonic generation via direct interaction of transverse optic (TO) phonons with photons in anharmonic lattice of ionic crystals is presented. There are two methods of supplying light energy for the excitation of TO lattice wave as a high frequency ultrasound: (A) incident light comes from the source outside the cavity? fulfilled with ionic crystal medium, (B) photon mode of the cavity possesses the gain of amplification by stimulated radiation of active atoms doping in the medium. More attention is drawn to the case (B). The working system of case (B), as a mixture of lasing action and ultrasonic generation, has the threshold phenomena like usual laser. And the linear stability analysis shows that the nonlineax phonon-photon coupling and the interaction among phonons themselves, both of which reflect the anharmonicity of lattice vibration, are necessary to the stable ultrasonic output. So this laser-ultrasonic generation mixture would be also a measure to investigate the lattice-dynamic nonlinearity and correlated electromagnetic properties of ionic crystals.

Poly(carbonate)-based ionic plastic crystal fast ion-conductor for solid-state rechargeable lithium batteries

Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial rechargeable lithium batteries(LIBs) due to their outstanding dissociation ability to lithium salts.However,volatility and fluidity result in their inevitable demerits like leakage and potential safety problem of the final LIBs.Here we for the first time device a subtle method to prepare a novel thermal-stable and non-fluid poly(carbonate) solid-state electrolyte to merge EC with lithium carriers.To this aim,a series of carbonate substituted imidazole ionic plastic crystals(G-NTOC) with different polymerization degrees have been synthesized.The resulting G-NTOC shows an excellent solid-state temperature window(R.T.-115℃).More importantly,the maximum ionic conductivity and lithium transference number of the prepared G-NTOC reach 0.36 × 10^(-3) S cm^(-1) and 0.523 at 30℃,respectively.Galvanostatic cycling test results reveal that the developed G-NTOC solid-state electrolytes are favorable to restraining the growth of lithium dendrite due to the excellent compatibility between the electrode and the produced plastic crystal electrolyte.The fabricated LiIG-NTOCILiFeP04 all-solid-state cell initially delivers a maximum discharge capacity of 152.1 mAh g^(-1) at the discharge rate of 0.1 C.After chargingdischarging the cell for 60 times,Coulombic efficiency of the solid-state cell still exceeds 97%.Notably,the LiIG-NTOCILiFeP04 cell can stably light a commercial LED with a rated power of 0.06 W for more than1 h at 30℃,and the output power nearly maintains unchanged with the charging-discharging cycling test,implying a sizeable potential application in the next generation of solid-state LIBs.

Solvent-free Synthesis,Crystal Structure and Thermal Stability of Ionic Liquid 1-Hexadecyl-3-methylimidazolium Bromide

Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate （[C16mim]Br·H2O）, 4 mm in length, was firstly obtained in the water-trichloromethane-toluene growth system （Vwater＇Vtrichloromethane＇Vtoluene = 0.1：1：2）. The crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P1, with a = 5.4962（15）, b = 7.839（2）, c = 27.279（8） A, α = 94.375, β = 91.500, γ = 101.999°, Z = 2, V = 1145.2（5） A3, C20H41BrN2O, Mr = 405.46, Dc = 1.176 Mg/m3, μ = 1.804 mm^-1, F（000） = 436, the final R = 0.0523 and wR = 0.1345. The 3D supramolecular structure is constructed through weak interactions between imidazolium cations, Br- anions and lattice water molecules. The long alkyl chain to the imidazolium ring and lattice water molecules play an important role in the self-assembly process. Moreover, it is proposed that [C16mim]Br in water has aggregation behavior and the possible self-assembled structure is the interdigitated pattern. Finally, thermal stability of [C16mim][Br]·H2O was also studied by DSC and TGA analysis.

Synthesis of Five-coordinated Anionic Tin(Ⅳ) Complexes and Crystal Structure of [(i-Pr)_2NH_2][PhSn( μ~2-SCH_2COO)_2]

Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.

The Effect of Ionic Liquids on the CaCO_3 Crystal Growth

In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.

Aminopropyl-containing ionic liquid based organosilica as a novel and efficient adsorbent for removal of crystal violet from wastewaters

Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 material was synthesized by hydrolysis and co-condensation of 1,3-bis-(3-trimethoxysilylpropyl)-imidazolium chloride(BTMSPIC) under acidic conditions followed by treatment with 3-aminopropyl-trimethoxysilane in toluene under reflux conditions. This material was characterized using scanning electron microscopy(SEM), diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS), thermal gravimetric analysis(TGA) and energy dispersive X-ray analysis(EDAX). The material was effectively used in the removal of crystal violet at ambient temperature and showed high capacity and stability under applied conditions. The efficacy of p H, contact time, adsorbent dose, initial dye concentration, temperature, and isotherm studies and the applicability of pseudo-first, second order and Elovich kinetic models have also been investigated.

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6(phCH_2NC_5H_5)3]·(H_2O)_4

A novel ionic compound [Fe（CN）6（phCH2NC5H5）3]·（H2O）4（Mr = 794.71） has been synthesized and its structure was characterized by IR, elemental analysis and X-my diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837（2）, b = 16.551（3）, c = 23.402（5） A, p = 97.531（4）°, V = 4161.0（15） A3, Z = 4, Dc = 1.269 g/cm^3, F（000） = 1668, p = 0.414 mm^-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three （phCH2N＋C5H5） ions, one [Fe（CN）6]^3- anion and four water molecules. According to the structural analysis, UFe（CN）6]^3- are linked together by O-H…N and O-H…O hydrogen bonds, but UFe（CN）6]^3- and [ （phCH2N＋ C5H5）3] ions are bound by electrostatic force to form an ionic compound.

Synthesis and Crystal Structure of a Neodymium Ionic Associate [Nd(dmso)_7Cl][Bph_4]_2

The title compound, [Nd(dmso) 7Cl][Bph 4] 2(dmso=dimethylsulfoxide, Bph 4=tetraphenylboron anion) was synthesized in organic solvent acetone/EtOH and the structure was determined by single crystal X ray diffraction. The crystal is triclinic with space group P 1, and the crystal data are as follows: a =1 2554(1) nm, b = 1 2799(1) nm, c =2 4598(3) nm; α =93 53(1)°, β =104 50(1)°, γ =112 77(1)°, V =3 4722(6) nm 3, Z =2, M r=1365 01, D c=1 306 g·cm -3 . The crystal is composed of a big cation [Nd(dmso) 7Cl] 2+ and two big anions [BPh 4] -. The Nd 3+ is coordinated by a chlorine atom and seven oxygen atoms from seven dimethylsulfoxides forming a distorted square antiprism coordination polyhedron,while the BPh - 4 anion is charge equilibrium ion.

离子化合物溶解性的热力学分析

无机盐的溶解性是化合物的重要性质之一,如何判断其溶解性大小是化学化工专业的新生较为关注的问题,本文从热力学角度分析离子晶体溶解包含晶体升华和离子水化两步过程,并分析两步过程中的焓效应和熵效应是如何影响离子化合物的溶解性,解释离子电荷及半径对其溶解性的影响,并借助离子晶体溶解过程的吉布斯自由能数据,总结其溶解性变化的基本规律,让学生理解物质性质变化规律的复杂性。

液晶电解质在锂离子电池中的研究进展

液晶电解质作为新型电解质材料,具有高离子导电性、优异的力学性能和热稳定性等优点,成为近年来锂离子电池领域研究的热点之一。液晶电解质可以通过自组装形成柱状相、近晶相或双连续立方相等结构,为锂离子的传输提供高效的离子传输通道。综述了液晶电解质在锂离子电池中的应用及研究进展,主要包括液晶电解质的基本概念和在锂离子电池中的研究进展,主要从离子电导率、电化学稳定性和充放电循环这3个方面来叙述。最后,对液晶电解质在锂离子电池领域未来的发展进行了展望。

基于斯卡那维模型的离子晶体介电性能的研究

本文采用玻恩圆周轨道极化模型、双原子分子离子位移极化模型,分别计算了NaCl晶体中各离子的电子位移极化率和离子位移极化率。进一步采用点偶极子近似和双原子分子平均场近似,考虑在极化离子所产生的附加电场的作用下,基于斯卡那维模型计算出包含不同离子数目的NaCl晶体的有效电场结构系数,得到了与实测值更为接近的介电常数,与将晶体内部的有效电场视为外施宏观平均电场的Born理论计算值进行对比,误差值从11.4%降至4.3%。研究结果提供了通过斯卡那维模型精确计算离子晶体介电性能的新思路。

Investigation of La_(9.33)Si_6O_(26) Oxygen Ionic Conductor

La9.335i6O26 oxygen ionic conductor was synthesized by solid state reaction method. Its structure was deter- mined by single-crystal X-ray diffraction analysis at room temperature. The results showed that La9.33Si6O26 oxide has the apatite structure with space group P63/m. AC impedance measurements indicated that the oxides sintered in nitrogen have much higher conductivity than those sintered in air. The effects of grain boundaries on the conductivity were discussed.

Oscillating Frequency Response of a Langasite Crystal Microbalance in Liquid Phase

The frequency responses of a langasite crystal microbalance （LCM） in liquid phase were investigated. It was shown that the LCM possessed much stronger oscillating ability in liquid phase than that of the commonly used quartz crystal microbalance （QCM）. The frequency shifts of the LCM to the changes in mass loading, as well as viscosity and density of the liquid were measured. The LCM was applied to monitor the adsorption process of an ionic liquid film to ethanol vapor.

Synthesis and Crystal Structure of Europium Associate(C_(34)H_(54)N_(2)O_(1)0)[Eu(NO_(3))_(5)]

The title compound, (C 34 H 54 N 2O 10 )[Eu(NO 3) 5](C 34 H 52 N 2O 10 =1,2 bis(2,3 benzo 10 aza 15 crown 5 N ethyleneoxy)ethane), was synthesized in acetonitrile solution and its crystal structure was determined by X ray analysis. The crystal crystallizes in monoclinic, space group P21/c with cell parameters a =1 1801(2) nm, b =2 3560(5) nm, c =1 7025(3) nm, β =99 67(3)°, V =4 6662(16) nm 3, Z =4, D c=1 581 g/cm 3. The europium ion is coordinated with ten oxygen atoms from five nitrato groups, and neither O atoms nor N atoms of the macrocyclic compound are bonded to the europium ion.

Correlation between Structure and Thermal Properties of N-vinyl-3-alkylimidazolium Magnetic Ionic Liquids

Influence of structural variations of N-vinylimidazolium tetrahalogenidoferrate(III) magnetic ionic liquids(MILs) on thermal properties was investigated. Using Gaussian09/B3 PW91/6-311 G(2d, p) density functional methods, the microstructure of the MILs were analyzed. With differential scanning calorimeter(DSC) and thermogravimetric analysis(TGA), the thermal properties of the MILs were performed. The results showed that the interaction energies of ion pairs decreased, the crystallization temperature increased first and then decreased, and the surfusion first decreased and then increased with the elongation of the alkyl chain length on cation;with the increase of Br atom, the interaction energies of ion pairs increased;the interaction energies of ion pairs increased in the MILs with the same cation or anion, the nature of polarity of MILs increased and the melting point rose;as the cation or anion in MILs had a smaller size, it could have the solidsolid transition temperature. The results indicated that the decomposition temperature with the same type of MILs increased with the interaction energies of ion pairs. The interaction energy of ion pairs can be used to illuminate the correlation between the thermal properties and the structure of MILs. ILs possesses the properties of macromolecular.