The first compound with an unusual type of anion, [Li(SR)2]–: bis­(μ2‐aqua‐d2)tetra­kis(aqua‐d2)dilithium(I) bis­[bis­(tri‐tert‐butoxy­silanethiol­ato‐κ2O,S)lithate(I)] dihydrate‐d2

The title complex, [Li₂(D₂O)₆][Li(C₉H₂₇SSiO₃)₂]₂·2D₂O, is the first compound with an S—M bond (M = alkali metal) within an unusual type of lithate anion, [Li(SR)₂]⁻ {where R is Si[OC(CH₃)₃]₃}. There is a centre of symmetry located in the middle of the Li₂O₂ ring of the cation. All Li atoms are four‐coordinate, with LiO₄ (cations) and LiO₂S₂ (anions) cores. The singly charged [Li(SR)₂]⁻ anions are well separated from the doubly charged [Li₂(D₂O)₆]²⁺ cations; the distance between Li atoms from differently charged ions is greater than 5 Å. Both ion types are held within an extended network of O—D⋯O and O—D⋯S hydrogen bonds.     

Preparation of ammonium intercalated vanadyl phosphate by redox intercalation and ion exchange

Redox intercalation of NH₄⁺ into vanadyl phosphate dihydrate (VOPO₄·2H₂O) leads to a two-phase (NH₄)_xVOPO₄·H₂O (x=0.2−0.9) compound with interlayer distances of 6.7 and 6.4 Å. Ammonium ions can be incorporated into the interlayer space of VOPO₄ also by an ion exchange, starting from alkali-metal redox-intercalated vanadyl phosphate Me_xVOPO₄·yH₂O (Me=Li, Na, K, Rb). Several phases are formed during the ion exchange, one of them with the interlayer distance corresponding to the original Me_xVOPO₄·yH₂O phase, the second one corresponding to formed (NH₄)_xVOPO₄·H₂O. In addition, a third phase is formed by the ion exchange when Li_0.98VOPO₄·1.98H₂O or Rb_0.60VOPO₄·1.3H₂O are used as starting compounds. An opposite ion exchange of NH₄⁺ for Me⁺ starting from (NH₄)_xVOPO₄·H₂O does not proceed.     

The structure of μ-oxo dimer of aluminium(III) porphyrin: a theoretical study

The gas-phase molecular structure of μ-oxo dimer of aluminium(III) porphyrin, (AlP)₂O, has been studied for the first time by density functional theory calculations using the B3LYP and M06 functionals and triple-ζ valence basis sets. The molecule has two conformers with equilibrium structures of D _4d and D _4h symmetries with parallel macrocycles and aluminium-oxygen distances of 1.680–1.684 Å (M06/cc-pVTZ). The aluminium atom lies out of the plane of the four central nitrogen atoms and forms a square-based pyramid with them, with the following parameters (M06/cc-pVTZ): r(Al–N) = 2.030–2.031 Å, r(N···N) = 2.803–2.804 Å (the side of the pyramid base), z(Al)–z(N) = 0.434–0.446 Å (the height of the pyramid).     

Hexalithium hexadecahydrate decavanadate, [Li6(H2O)16V10O28]n

The novel title compound, poly­[octa‐μ‐aqua‐octa­aqua‐μ‐decavanadato‐hexalithium], contains [V₁₀O₂₈]⁶⁻ polyanions with 2/m symmetry linked by centrosymmetric [Li₆(H₂O)₁₆]⁶⁺ cation chains. The [V₁₀O₂₈]⁶⁻ polyanions form a two‐dimensional network with [Li₆(H₂O)₁₆]⁶⁺ chains via O‐polyanion–Li‐chain coordination, with Li—O bond lengths in the range 2.007 (5)–2.016 (5) Å. The hexalithium hexadecahydrate chain is composed of a centrosymmetric pair of LiO₆ octahedra and four distorted LiO₄ tetrahedra. Hydro­gen bonds occur between the polyanion and the Li‐based chains, and within the Li‐based chains.     

Synthesis,characterization, and thermochemical property of a novel mixed alkali metal borate: NaCs[B10O14(OH)4]

A novel mixed alkali metal hydrated borate NaCs[B₁₀O₁₄(OH)₄] was synthesized under hydrothermal conditions. Its structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR spectroscopy, TG-DTA, powder X-ray diffraction, and chemical analysis. NaCs[B₁₀O₁₄(OH)₄] crystallizes in monoclinic space group P2/c with a = 7.6588(3) Å, b = 9.0074(3) Å, c = 11.8708(6) Å, and β = 115.682(3)°. The crystal structure of NaCs[B₁₀O₁₄(OH)₄] consists of Na–O, Cs–O polyhedral, and [B₁₀O₁₄(OH)₄]^2? polyborate anions. [B₁₀O₁₄(OH)₄]^2? units are connected together through common oxygen atoms forming a 1D helical chain-like structure, which are further connected by O–H···O hydrogen bonds forming a 3D supramolecular structure. Through a designed thermochemical cycle, the standard molar enthalpy of formation of this borate was determined to be ?7888.6 ± 8.1 kJ mol^?1 by using a heat conduction microcalorimeter.     

Zur Kenntnis des Natriumthioferrates(III)

The mixed valency compound Na₃Fe₂S₄, which is also formed in iron-sodium polysulfide melts, is oxidized and hydrated to NaFeS₂·H₂O (x ≈ 2) on air. It is shown by TGA that this hydrate loses the water reversibly between 80–140 °C. A crystal structure model for the water free phase NaFeS₂ is proposed (space group I 222,a=6.25 Å,b=10.83 Å,c=5.40 Å). The formation of NaFeS₂·xH₂O from Na₃Fe₂S₄ and the reversible phase transformation between NaFeS₂·xH₂O and NaFeS₂ are topotactic. Na⁺ ions in NaFeS₂·xH₂O are easily exchanged against K⁺, Rb⁺, Cs⁺, Tl⁺, Ca²⁺, Sr²⁺, and Ba²⁺. The high chemical reactivity of the sodium thioferrates is discussed and their crystal structures are compared with the other alkali metal thioferrate structures.     

Hydrogen Bonding and Solvent Effects on Complexation of Alkali Metal Cations by Lower Rim Calix[4]arene Tetra(O-[N-acetyl-D-phenylglycine methyl ester]) Derivative

Complexation of alkali metal cations with 5,11,17,23-tetra-tert-butyl-26,28,25,27-tetrakis(O-methyl-D-α-phenylglycylcarbonylmethoxy)calix[4]arene (L) was studied by means of spectrophotometric, conductometric and potentiometric titrations at 25 °C. The solvent effect on the binding ability of L was examined by using two solvents with different affinities for hydrogen bonding, viz. methanol and acetonitrile. Despite the presence of intramolecular NH···O=C hydrogen bonds in L, which need to be disrupted to allow metal ion binding, this calix[4]arene amino acid derivative was shown to be an efficient binder for smaller Li⁺ and Na⁺ cations in acetonitrile (lg K _LiL  > 5, lg K _NaL  = 7.66), moderately efficient for K⁺ (lg K _KL  = 4.62), whereas larger Rb⁺ and Cs⁺ did not fit in its hydrophilic cavity. The complex stabilities in methanol were significantly lower (lg K _NaL  =  4.45, lg K _KL  = 2.48). That could be explained by different solvation of the cations and by competition between the cations and methanol molecules (via hydrogen bonds) for amide carbonyl oxygens. The influence of cation solvation on complex stability was most pronounced in the case of Li⁺ for which, contrary to the quite stable LiL ⁺ complex in acetonitrile, no complexation was observed in methanol under the conditions used.     

Synergistic extraction of some univalent cations into nitrobenzene by using cesium dicarbollylcobaltate and dibenzo-30-crown-10

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq) + 1·Cs⁺(nb) ? 1·M⁺(nb) + Cs⁺(aq) taking place in the two-phase water–nitrobenzene system (M⁺ = Li⁺, Na⁺, H⁺, NH₄ ⁺, Ag⁺, K⁺, Rb⁺, Tl⁺; 1 = dibenzo-30-crown-10; aq = aqueous phase, nb = nitrobenzene phase) were determined. Furthermore, the stability constants of the 1·M⁺ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the series of Cs⁺ < H⁺, Ag⁺ < NH₄ ⁺ < Na⁺ < Rb⁺ < Li⁺ < K⁺, Tl⁺.     

Two New One-Dimensional Chain-Like Compounds Constructed from the Sandwich-Type Polyoxotungstate Clusters

Two new one-dimensional chain-like compounds, K₄Na₄[Mn₂(H₂O)₈Mn₄(H₂O)₂(GeW₉O₃₄)₂] · 20.5H₂O (1) and K₂Na₄Cu₂(H₂O)₁₂[Cu(H₂O)₂Cu₄(H₂O)₂(SiW₉O₃₄)₂] · 15H₂O (2), constructed from the sandwich-type clusters, have been obtained by the routine synthetic reactions in aqueous solutions, and their structures were determined by X-ray single crystal diffraction analysis. The crystal data is following: for 1, space group, monoclinic, P _21/n, a = 16.693(3) Å, b = 14.935(3) Å, c = 20.090(4) Å, β = 92.23(3)°, V = 5004.7(17) ų, Z = 2; For 2, space group, triclinic, P _?1, a = 11.744(2) Å, b = 13.415(3) Å, c = 17.609(4) Å, α = 73.08(3)°, β = 82.68(3)°, γ = 65.18(3)°, V = 2409.1(8) ų, Z = 1. The crystal structure of 1 shows a 1D ladder-like chain, built up of the sandwich anions [Mn₄(H₂O)₂(GeW₉O₃₄)₂]^12? and the Mn²⁺ ions. Compound 2 is a polymeric chain, composed of the Cu-substituted sandwich-type anions [Cu₄(H₂O)₂(SiW₉O₃₄)₂]^12? linked by the Cu(H₂O)₄ clusters. These extended materials based on the sandwich-type polyoxoanions are rarely reported in the POM chemistry.     

Two Hexa-Ni-Substituted AsW9O34 Clusters Functionalized by Organic Ligands

Hydrothermal reactions of trilacunary precursor A-α-AsW₉O₃₄ ^9? polyoxoanions and nickel ions in the presence of ethylenediamine (en = ethylenediamine) led to two new hexa-Ni-substituted Keggin-type tungstoarsenates [Ni₆(μ ₃-OH)₃(en)₃(H₂O)₆(B-α-AsW₉O₃₄)]·6H₂O (1) and [Ni₆(μ ₃-OH)₃(en)₃(H₂O)₆(B-α-AsW₉O₃₄)]·10H₂O (2), which have been characterized by elemental analyses, IR spectra, powder X-ray diffraction, thermogravimetric analyses and single-crystal X-ray diffraction. Crystal data for 1: hexagonal, R3c, a = b = 20.4379(5) Å, c = 21.5062(6) Å, β = 120º, V = 7779.8 (3) Å³ and Z = 6; for 2: momoclinic, P2₁/c, a = 13.4200(3) Å, b = 19.1428(5) Å, c = 22.8845(9) Å, β = 112.403(3)º, V = 5435.2(3) Å³ and Z = 4. Structural analyses reveal that the [Ni₆(μ ₃-OH)₃(B-α-AsW₉O₃₄)] clusters in 1 and 2 are covalently functionalized by neutral en ligands, in which two similar {Ni₆(μ ₃-OH)₃(en)₃(H₂O)₆}⁹⁺ cores have been observed by our lab. Notably, 1 and 2 represent the highest number of substituted transition metal ions in all known lacunary Keggin-type polyoxotungstoarsenate monomers.     

Neutron diffraction study of uranyl oxalate [UO2(C2O4)(D2O)] · 2D2O

A powdered sample of uranyl oxalate [UO₂(C₂O₄)(D₂O)] · 2D₂O (compound I) is studied using neutron diffraction. The crystals are monoclinic, space group P2₁/c, with a = 5.608(1) Å, b = 17.016(3) Å, c = 9.410(2) Å, β = 98.9369(2)°, Z = 4, R _f = 0.042, R _I = 0.054, x ² = 1.5. The main structural units of the crystals are [UO₂(C₂O₄)(D₂O)] chains. These chains, which belong to the AK⁰²M¹ (A = UO ₂ ²⁺ ) crystal-chemical group of the uranyl complexes, lie parallel to [101]. The water molecules in the crystals of I are hydrogen-bonded into zigzag chains running along [100]. Since each third oxygen atom of the chain formed of water molecules is coordinated to the uranium atom, the uranyl oxalate chains are linked into {[UO₂(C₂O₄)(D₂O)] · 2D₂O} layers that lie normal to [010]. The layers are linked into the framework through interlayer hydrogen bonds (D₂O)O-D···O (oxalate).     

Adsorption of Li by a lithium ion-sieve using a buffer system and application for the recovery of Li from a spent lithium-ion battery

A lithium ion-sieve manganese oxide (MO) derived from Li-enriched MO was prepared by the glycolic acid complexation method. The Li adsorption performance in a LiCl–NH₃·H₂O–NH₄Cl buffer solution, simulated a spent lithium-ion battery (LIB) processing solution, and actual spent LIB processing solution were studied. An adsorption capacity of 27.4 mg/g was observed in the LiCl–NH₃·H₂O–NH₄Cl buffer solution (Li concentration of 0.2 mol/L, pH?=?9), and the adsorption behavior conformed to the Langmuir adsorption isotherm equation with a linear correlation coefficient (R²) of 0.9996. An adsorption capacity of 19 mg/g was observed in the simulated buffer spent battery solution (Li concentration of 0.15 mol/L, pH?=?7), and an adsorption capacity of 17.8 mg/g was observed in the actual spent battery solution (Li concentration of 0.15 mol/L, pH?=?7). X-ray diffraction, scanning electron microscope, and infrared spectrum results revealed that the structure and morphology of MO are stable before and after adsorption, and the adsorption of MO in all of the abovementioned buffer systems conforms to the Li⁺–H⁺ ion-exchange reaction mechanism. The lithium ion-sieve MO demonstrates promise for the recovery of lithium from spent LIBs.     

Synthesen und Reaktionen von Aluminiumalkoxid‐Verbindungen

Syntheses and Reactions of Aluminium Alkoxide Compounds Al(O^cHex)₃ ( 1 ) can be synthesized by the reaction of Al with cyclohexanol under evolving of H₂ in boiling xylene. [Li{Al(OCH₂Ph)₄}] ( 2 ) was obtained by treatment of PhCH₂OH with a 1 M solution of LiAlH₄ in THF. [{(THF)Li}₂{Al(O^tBu)₄}Cl] ( 3 ) is the result of the reaction of four equivalents of LiO^tBu on AlCl₃ in THF. 3 is the educt for the reactions with the Lewis‐acids InCl₃ and FeCl₃ in THF leading to the metalates [{(THF)₂Li}₂{Al(O^tBu)₄}] · [MCl₄] [M = In ( 4 ), Fe ( 5 )]. The attempt to react InCl₃ with four equivalents of LiO^tBu leads to only one isolated and characterized product, the complex [Li₄(O^tBu)₃(THF)₃Cl]₂ · THF ( 6 · THF), which can also be synthesized by the treatment of LiCl with three equivalents of LiO^tBu in THF. 1–6 · THF were characterized by NMR, IR and MS techniques as well as by X‐ray structure determinations. According to them, 1 , which is tetrameric in solution, is the first structurally characterized example of the proposed trimer form of aluminium alkoxides [ROAl{Al(OR)₄}₂] with a central trigonal bipyramidal coordinated Al atom. 2 forms a coordination polymer with a distorted tetrahedral coordination sphere of Li and Al, running along [100]. The trinuclear structure skeleton [{(THF)₂Li}₂{Al(O^tBu)₄}]⁺ is still present in the isotypical metalates 4 and 5 . The counter ions [MCl₄]^– possess nearly T_d symmetry. The remarkable structural motif of 6 · THF are two heterocubanes [Li₄(O^tBu)₃(THF)₃Cl] dimerized by Li–Cl bonds.     

The structure of [M(H2O)6][LiFeIII(ox)3] (M=MnII,FeII) – A heterobimetallic 2-D tris(oxalato) framework compound

[Mn^II_xFe^II_1?x(H₂O)₆][LiFe^III(ox)₃] (with 0 ≤ x ≤ 1) crystallizes in the space group P31c with a = 9.341(3) Å, c = 10.226(3) Å, c/a = 1.0947, and V = 772.8(5) Å³ for Z = 2. The compound has a layered structure with two enantiomeric layers per unit cell. The layers are built up by an iron and lithium oxalate framework with intercalated M(II)-water octahedra of the formula [Mn^II_xFe^II_1?x(H₂O)₆][M^IM^III(ox)₃]. The value of x cannot be specified at present. The structure displays intermolecular hydrogen bonding between the layers.     

Thermochemical property of a microporous material for mixed metal borate of Li2Sr4B12O23

A pure mixed alkali–alkaline earth metal borate of Li₂Sr₄B₁₂O₂₃ with microporous structure has been synthesized by high-temperature solid state reaction, and characterized by XRD, FT-IR, TG techniques, and chemical analysis. The molar enthalpies of solution of Li₂Sr₄B₁₂O₂₃ in 1 mol L^?1 HCl(aq), and of SrCl₂·H₂O(s) in [1 mol L^?1 HCl + H₃BO₃ + LiCl·H₂O](aq) have been determined by microcalorimeter at 298.15 K, respectively. From these data and with the incorporation of the previously determined enthalpies of solution of H₃BO₃(s) in 1 mol L^?1 HCl(aq), and of LiCl·H₂O(s) in [1 mol L^?1HCl + H₃BO₃](aq), together with the use of the standard molar enthalpies of formation for SrCl₂·6H₂O(s), LiCl·H₂O(s), H₃BO₃(s), HCl(aq), and H₂O(l), the standard molar enthalpy of formation of ?(11,534.0 ± 10.0) kJ mol^?1 for Li₂Sr₄B₁₂O₂₃ was obtained on the basis of the appropriate thermochemical cycle.     

Amino Acid Functionalization of {Ni6PW9}-Based Clusters Under Hydrothermal Conditions

Two novel hexa-nickel(II)-substituted Keggin-type {Ni₆PW₉}-based tungstophosphates [Ni₆(μ ₃-Tris)(en)₃(Pr)(damp)(H₂O)₂(B-α-PW₉O₃₄)]·10H₂O (1) and [Ni₆(μ ₃-Tris)(en)₃(damp)₂(H₂O)₂(B-α-PW₉O₃₄)]·7H₂O (2) (en = ethylenediamine, Pr = CH₃CH₂COO^?, damp = 2-aminoisobutyrate, Tris = pentaerythritol) were hydrothermally synthesized and characterized by IR spectra, elemental analyses, powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray diffraction. Crystal data for 1: orthorhombic, Pca2₁, a = 21.6962(7) Å, b = 20.6398(5) Å, c = 14.7825(4) Å, β = 90º, V = 6619.7(3) Å³, Z = 4; for 2: orthorhombic, Pca2₁, a = 21.6978(9) Å, b = 20.6658(7) Å, c = 14.7767(4) Å, β = 90º, V = 6625.9(4) Å³, Z = 4. 1 consists of a {Ni₆(μ ₃-Tris)(en)₃(Pr)(damp)(H₂O)₂}⁹⁺ core and a [B-α-PW₉O₃₄]^9? (PW₉) unit and is covalently functionalized by one Pr and one damp, as well as en and Tris ligands. The structure of 2 is the same to 1 except that the Pr anion in 1 is substituted by the other damp ligand. Most interestingly, 1 contains four kinds of organic ligands, while 2 includes three kinds of organic ligands, which are first observed in polyoxometalate chemistry.     

A three-dimensional porous and magnetic framework constructed from copper salt and 5-Methyltetrazole: [Cu8(Metz)9](OH)·xH2O

A new compound of [Cu₈(Metz)₉](OH)·xH₂O (x≈3) (1) (Metz = 5-Methyltetrazole) has been prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The crystal is of hexagonal, space group P6₃/m with a = b = 13.988(1) Å, c = 16.309(2) Å, α = β = 90°, γ = 120°, V = 2 763.5 (4) Å³, Mr = 1327.13, D _c = 1.595 g cm^?3, Z = 2, F(000) = 1 316, μ = 3.076 mm^?1, the final R = 0.0494 and wR = 0.1532 for 1,731 observed reflections (I > 2σ(I)). In this compound, the [(Cu^II)₂(Cu^I)₆(Metz)₉]⁺ cationic clusters are connected together through Cu^I cations and Metz ligands and result in a three-dimensional framework. Remarkable, three-dimensional intersecting channels exist in it. The variable temperature magnetic investigations indicate that 1 exhibits typical antiferromagnetic behaviors. N₂ gas adsorption measurements at 77 K showed that compound 1 possesses permanent porosities.     

三维有序大孔LiAlMnO_4的合成及其Li~+脱嵌行为(英文)

<正>In the past half century,several methods like solvent extraction[1],precipitation[2]and ion exchange[3,4]have been extensively studied for lithium recovery from seawater and salt lake brine.     

Ab initio interaction and spectral properties of CO+–He

In this contribution, ab initio methods have been used to study the open-shell CO⁺–He van der Waals (vdW) complex in both the ground and the first Π excited electronic state. Calculations were performed at the UCCSD(T) level of theory in the framework of the supermolecule approach using the cc-pVTZ basis set complemented with a set of standard bond functions in the middle of the vdW bond. Calculations predict a most-stable equilibrium conformation with β e=45°, R _e =2.85 Å and D _e =275 cm^?1 for the ground CO⁺(X²Σ)–He(¹S) state and β e=90°, R _e =2.70 Å and D _e =218 cm^?1 for the excited CO ⁺(A²Π)–He(¹S) state. The dipole moment μ and independent components of the field polarizability α of the CO ⁺–He vdW complex have been studied at the calculated equilibrium geometry of these states. The vertical excitation energies from the ground CO⁺(X ²Σ)–He(¹S) to the excited CO⁺(A²Π)–He (¹S) electronic state and corresponding shifts in the fluorescent spectrum with respect to the isolated CO⁺ molecule are also presented     

[Mo4O4(μ-S)4(μ-OH)2(μ-H2O)(H2O)2(pba)]2−: An Original Coordination Mode for the Ligand 1,3-Propylenebis(Oxamate)

The novel polyoxothioanion [Mo₄S₄O₄(OH)₂(OH₂)₃pba]^2? where pba^4? ligand is the 1,3-propylenebis(oxamate), was prepared by reacting Mo₁₂S₁₂O₁₂(OH)₁₂(OH₂)₆ ring with [Cu-pba]^2? in aqueous medium. NaK[Mo₄O₄(μ-S)₄(μ-OH)₂(μ-H₂O)(H₂O)₂(pba)] ·7H₂O was isolated in the solid state and fully characterized by X-ray diffraction study (tetragonal, P4(2)/m [a=20.4962(4) Å; b=20.4962(4) Å; c=14.7013(5) Å). The molecular structure consists of an arc cycle shape tetranuclear enchainment {Mo₄S₄O₄(OH)₂ (OH₂)₃} closed by a pba^4? ligand. The 3-D packing, resulting from the connection between K⁺ and Na⁺ and the coordination complex {Mo₄-pba]^2? is described. The ¹H-NMR characterization of the complex in aqueous solution is given. The ¹H-NMR spectrum exhibits four signals assigned to four enantiotopic protons of the alkyl chain of the pba^4? ligand and is in agreement with crystal structure of the complex [Mo₄-pba]^2?. The compound was also characterized by infrared spectroscopy.