Synthese und Kristallstruktur von Ba25Cu142+Cu43+Zn4O49

Synthesis and Crystal Structure of Ba₂₅Cu₁₄²⁺Cu₄³⁺Zn₄O₄₉ Single crystals of Ba₂₅Cu₁₄²⁺Cu₄³⁺Zn₄O₄₉ were prepared with solid state and flux reactions. X-ray investigations show tetragonal symmetry, space group D⁷_4th–P4/nmm, a = 18.2146, c = 9.3230 Å, Z = 2. The hitherto unknown structure type shows copper in square pyramids and planar polygones, connected to six member rings or Cu₅O₂₀ groups. Slightly bent Cu₅O₁₂ groups produced by edge connection of five CuO₄ polygones are connected with ZnO₄ tetrahedra forming Cu₅Zn₄O₂₀ units. The complicated structure is shown step by step.     

über die Reaktionen von CH3OCl,CF3OCl,CF3OF und CF3OH mit dem supersauren System HF/MF5 (M = As,Sb) Darstellung und Charakterisierung von CH3OCl(H)+MF6− und CF3OCl(H)+MF6−

On the Reactions of CH₃OCl, CF₃OCl, CF₃OF, and CF₃OH with the Superacid System HF/MF₅ (M = As, Sb). Preparation and Characterization of CH₃OCl(H)⁺MF₆^? and CF₃OCl(H)⁺MF₆^? The preparation of the chlorine oxoniumsalts CH₃OCl(H)⁺MF₆^? and CF₃OCl(H)⁺MF₆^? by protonation of CH₃OCl and CF₃OCl in the superacid solution of HF/MF₅ (M = As, Sb) is described. However CF₃OF and CF₃OH have not been protonated under the same conditions. In the case of CF₃OH the formation of F₂CO · MF₅ is observed. The novel compounds are characterized by nmr- and vibrational spectroscopy.     

Cinnamal Sensing and Luminescence Color Tuning in a Series of Rare-Earth Metal−Organic Frameworks with Trans-1,4-cyclohexanedicarboxylate

Three isostructural metal–organic frameworks ([Ln₂(phen)₂(NO₃)₂(chdc)₂]·2DMF (Ln³⁺ = Y³⁺ for 1, Eu³⁺ for 2 or Tb³⁺ for 3; phen = 1,10-phenanthroline; H₂chdc = trans-1,4-cyclohexanedicarboxylic acid) were synthesized and characterized. The compounds are based on a binuclear block {M₂(phen)₂(NO₃)₂(OOCR)₄} assembled into a two-dime nsional square-grid network containing tetragonal channels with 26% total solvent-accessible volume. Yttrium (1)-, europium (2)- and terbium (3)-based structures emit in the blue, red and green regions, respectively, representing the basic colors of the standard RGB matrix. A doping of Eu³⁺ and/or Tb³⁺ centers into the Y³⁺-based phase led to mixed-metal compositions with tunable emission color and high quantum yields (QY) up to 84%. The bright luminescence of a suspension of microcrystalline 3 in DMF (QY = 78%) is effectively quenched by diluted cinnamaldehyde (cinnamal) solutions at millimolar concentrations, suggesting a convenient and analytically viable sensing method for this important chemical.     

基于二苯基咪唑的氟离子荧光探针的合成及性能

本文设计制备了一种二苯基咪唑衍生化的荧光探针1,利用紫外-可见吸收光谱和荧光光谱研究探针对阴离子的选择性。在探针的乙腈溶液中引入F_^-后,606 nm处的荧光强度发生明显的猝灭,并且可通过裸眼识别F_^-。探针对F_^-的识别表现出高灵敏性以及较好的抗干扰能力,检测限可低至9.43×10_^-8 mol L_^-1。此外,制备的1+F_^-体系对湿度较敏感,在水分影响下该体系的颜色和荧光强度能够实现可逆恢复。     

Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage

A calix-shaped polyoxometalate, [V₁₂O₃₂]⁴⁻ (V12), stabilizes an anion moiety in its central cavity. This molecule-sized container has the potential to control the reactivity of an anion. The highly-reactive cyanate is smoothly trapped by V12 to form [V₁₂O₃₂(CN)]⁵⁻. In the CH₃NO₂ solution, cyanate abstracts protons from CH₃NO₂, and the resultant CH₂NO₂⁻ is stabilized in V12 to form [V₁₂O₃₂(CH₂NO₂)]⁵⁻ (V12(CH₂NO₂)). A crystallographic analysis revealed the double-bond characteristic short bond distance of 1.248 Å between the carbon and nitrogen atoms in the nitromethane anion in V12. ¹H and ¹³C NMR studies showed that the nitromethane anion in V12 must not be exchanged with the nitromethane solvent. Thus, the V12 container restrains the reactivity of anionic species.     

Interaction of iron carbonyls with Lewis bases

The interaction of iron carbonyls Fe _n (CO) _m (wheren = 1,m = 5;n = 2,m = 9;n = 3,m = 12) with anionic Lewis bases (H^–, F^–, Cl^–, Br^– , I^–, CN^–, SCN^–, N₃ ^–, MeSO₃ ^–, MeCO₂ ^–, CF₃CO₂ ^–, S₂ ^–, CO₃ ^2–, and SO₄ ^2–) passes through two-stage redox-disproportionation. The first stage is the formation of an iron carbonyl-base complex, [Fe _n (CO) _m–1C(O)L]^–, and the second is a single-electron reduction of this complex by another molecule of the initial iron carbonyl, giving rise to Fe(l) and Fe(–l) derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 248–249, January, 1996.     

Synthesis and investigation of mono- and binuclear cyano-bridged complexes of rhodium,ruthenium, and palladium

Binuclear Rh^III and Ru^II complexes of the [M¹-CN-M²]⁺BF ₄ ^– (M¹ and/or M² are (⁵-Cp)(³-C₃H₅)Rh and (⁶-C₆H₆)(³-C₃H₅)Ru) type, heteronuclear organometallic compound (⁵-Cp)(³-C₃H₅)RhCNPd(³-C₃H₅)Cl, and mononuclear Rh^III and Ru^II complexes [(³-C₃H₅)LM(MeCN)]⁺ _BF4 ^– (M = Rh, L = ⁵-Cp; M = Ru, L = ⁶-C₆H₆) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(⁵-Cp)(³-C₃H₅)Rh(MeCN)]⁺ _BF4 ^– with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995.     

ChemInform Abstract: Protonated Nitric Acid. Structure and Relative Stability of Isomeric H2NO+ 3 Ions in the Gas Phase.

Gaseous H₂NO₃⁺ ions are generated by direct protonation of HNO₃ by H3⁺, H₃O⁺ and CH₅⁺ and by protonation of C₂H₅ONO₂ followed by C₂H₄ loss.     

The ESR study of the influence of fluorinated alcohols on spin-adducts of phosphoryl radicals with C60 and C70: a change of magnetic resonance parameters and exclusive formation of monoadducts

Complex formation of^.C₆₀P(O)(OPrⁱ)₂ or three isomers of^.C₇₀P(O)(OPrⁱ)₂ with fluorinated alcohols CF₃CH₂OH (1), (CF₃)₃COH (2), and (CF₃)₂CHOH (3) results in an increase in the hyperfine splitting constants with the³¹P nucleus by approximately 3–4 G. Only monoadducts are formed when alcohols1–3 are added to toluene saturated solutions of Hg[P(O)(OPrⁱ)₂]₂ and C₆₀ under photochemical conditions of multi-addition of phosphoryl radicals to C₆₀. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1869–1871, September, 1998.     

Über die Darstellung der Pnikogenoniumsalze AsH4+SbF6−, AsH4+AsF6−, SbH4+SbF6−

On the Preparation of Pnikogenonium Salts AsH₄⁺SbF₆^?, AsH₄⁺AsF₆^?, SbH₄⁺SbF₆^? The preparation of the pnikogenonium salts AsH₄⁺SbF₆^?, AsH₄⁺AsF₆^? and SbH₄⁺SbF₆^? by protonation from the hydrides AsH₃, SbH₃ in superacidic systems HF/SbF₅ and HF/AsF₅, resp. is reported. The salts are characterized by vibrational and mass spectra. A general valence force field is calculated. The following onium ions are know as hexafluoroantimonate:      

Komplexchemie P‐reicher Phosphane und Silylphosphane. XXII. Die Bildung von [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]aus (Me3Si)tBuP–P=P(Me)tBu2 und [η2‐{C2H4}Pt(PR3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η²‐{^tBu–P=P–SiMe₃}Pt(PR₃)₂] from (Me₃Si)^tBuP–P=P(Me)^tBu₂ and [η²‐{C₂H₄}Pt(PR₃)₂] (Me₃Si)^tBuP–P = P(Me)^tBu₂ reacts with [η²‐{C₂H₄}Pt(PR₃)₂] yielding [η²‐{^tBu–P=P–SiMe₃}Pt(PR₃)₂]. However, there is no indication for an isomer which would be the analogue to the well known [η²‐{^tBu₂P–P}Pt(PPh₃)₂]. The syntheses and NMR data of [η²‐{^tBu–P=P–SiMe₃}Pt(PPh₃)₂] and [η²‐{^tBu–P=P–SiMe₃}Pt(PMe₃)₂] as well as the results of the single crystal structure determination of [η²‐{^tBu–P=P–SiMe₃}Pt(PPh₃)₂] are reported.     

Ein Neues gemischtvalentes Oxoosmat(VI,VII): Sr11Os26+Os27+O24

A New Mixed Valenced Oxoosmate(VI, VII): Sr₁₁Os₂⁶⁺Os₂⁷⁺O₂₄ . Single crystals of Sr₁₁Os₂⁶⁺Os₂⁷⁺O₂₄ were prepared in closed silver bombs using SrO, osmium and an extend of KO₂. It crystallizes with monoclinic symmetry, space group C–I12/a1 a = 11.703; b = 16.058; c = 11.696 Å; β = 90.03°; Z = 4. Sr₁₁Os₂⁶⁺Os₂⁷⁺O₂₄ shows a new crystal structure characterized by a [Sr₁₁O₂₄]^26? network and incorporated Os⁶⁺ and Os⁷⁺ ions. Calculations of the coulombterm of lattice energy shows an orderer distribution of the two oxidation states of osmium.     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).     

ChemInform Abstract: Theoretical Study on Electronic Structures of AuF6 and Its Anions.

SCF-MO and CI calculations on AuFn6^- (n = 0-3) (model potential method) show that the AuF₆^- anion has the lowest minimum energy in this series and the energy of the AuF₆^3- anion is ∼ 4 eV higher than that of AuF₆^- and AuF₆^2- at their equilibrium positions.     

Eu3+ und Eu2+ in Oxometallaten der Zusammensetzung MBeLn2O5: SrBeEu2O5 und EuBeNd2O5

Eu³⁺ and Eu²⁺ in Oxides of the Composition MBeLn₂O₅: SrBeEu₂O₅ and EuBeNd₂O₅ Single crystals of (I): SrBeEu₂O₅ and (II): EuBeNd₂O₅ were prepared by CO₂-LASER (I) in air and plasma torch (II) technique in H₂ atmosphere. X-ray investigations led to orthorhombic symmetry, space group D-Pnma; (I): a = 9.488, b = 7.156, c = 6.495 Å; (II): a = 9.534, b = 7.225, c = 6.544 Å, Z = 4. Sr²⁺ and Eu³⁺ as well as Eu²⁺ and Nd³⁺ are in statistical distribution within a Kagomé framework. Both compounds are discussed with respect to the monoclinic form of MBeLn₂O₅.     

Ein Beitrag über CuPrMo2O8 und CuTbMo2O8

A Contribution on CuPrMo₂O₈ and CuTbMo₂O₈ Single crystals of (I): CuPrMo₂O₈ and (II): CuTbMo₂O₈ were prepared by solid state reactions in closed copper tubes. They crystallize with orthorhombic symmetry, space group D-Pbca, (I): a = 10.4114, b = 9.8917, c = 14.8287 Å, (II): a = 10.2243, b = 9.7385, c = 14.6000, Z = 8. Both compounds are isotypic to CuYMo₂O₈, showing isolated MoO₄ tetrahedra, square antiprismatic coordination of Ln³⁺ and Cu⁺ besides one edge of an O^2? triangle. Calculations of the coulombterm of lattice energy support the oxidation state Cu²⁺ in combination with mixed valences of Mo⁶⁺ and Mo⁵⁺ on the molybdenum point positions.     

Ruthenium complexes with heteropoly anion PW11O39 7− and their redox properties

A new heteropoly complex PW₁₁Ru^IV and complexes of Ru^II, Ru^III and Ru^V based thereon have been obtained. Using specrophotometry the states of Ru^III and Ru^IV complexes in solution, the pH range of their stability, and the interaction of PW₁₁Ru^IV with ClO₄ ^–,SO₄ ^2–, Cl^– ions have been studied. A conclusion has been thus made that the ruthenium ion in such a complex is not incorporated in the heteropolyanion lattice, but is attached only to its external oxygen atoms. Kinetics of oxidation of PW₁₁Ru^IV and PW₁₁Ru^III with potassium chlorate have been studied. The activation energy and pre-exponential factor have been found for the reaction. The possibility that ClO₄ ^– and ClO₃ ^– in aqueous solutions can be activated by PW₁₁Ru^II with the former and by PW₁₁Ru^III and PW₁₁Ru^IV with the latter has been demonstrated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1363–1369, August, 1993.The authors wish to thank I. L. Krayevskaya and V. M. Novopashina for X-ray fluorescence and ionic chromatographic analyses, respectively.     

ChemInform Abstract: Stability of B12(CN)122‐: Implications for Lithium and Magnesium Ion Batteries.

DFT calculations are used to calculate the binding energies of the second electron of the closo‐borane B₁₂H₁₂^2‐ and B₁₂(CN)₁₂^2‐.     

121,123Sb NQR study of antimony(III) fluoride complexes

Antimony(III) complexes with nitrogen-containing ligands: 2SbF₃·Gly, SbF₃·Gly, SbF₃·2NA, SbFO·Gly, MSb₂F₇ (M=Et₂NH₂, Bu₄N, HNA⁺), MSbF₄ (M=Et₂NH₂, Pr₂NH₂, Bu₄N, HNA⁺, HGly⁺), M₂SbF₅ (M=Et₂NH₂ and Pr₂NH₂), where Gly is glycine (⁺NH₃CH₂COO⁻) and NA is nicotinamide (β-C₅H₄NCONH₂), were studied by^121,123Sb NQR spectroscopy at 77 K. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2232–2236, November, 1998.     

ChemInform Abstract: Unusual Inorganic Biradicals: A Theoretical Analysis.

Quantum chemical calculations at the CASSCF level of theory on the O₃‐homologous molecules CX₂^2‐, NX₂^‐, X₃, OX₂, and FX₂⁺ (X: O, S, Se, Te, Po) indicate that the triatomic inorganic biradicals in the FX₂⁺ series have unusually high biradical character.