General route to three-dimensional framework uranyl transition metal phosphates with atypical structural motifs: the case examples of Cs2{(UO2)4[Co(H2O)2]2(HPO4)(PO4)4} and Cs3+x[(UO2)3CuH4-x(PO4)5].H2O

The reaction of UO2(NO3)2.6H2O with Co or Cu metal, phosphoric acid, and CsCl under mild hydrothermal conditions results in the formation of Cs2{(UO2)4[Co(H2O)2(HPO4)(PO4)4} (1) or Cs(3+x)[(UO2)3CuH(4-x)(PO4)5].H2O (2). The structure of 1 contains uranium atoms in pentagonal bipyramidal and hexagonal bipyramidal environments. The interaction of the uranyl cations and phosphate anions creates layers in the [ab] plane. The uranyl phosphate layers are joined together by octahedral Co centers wherein the Co is bound by phosphate and two cis water molecules. In addition, the Co ions are also ligated by a uranyl oxo atom. The presence of these octahedral building units stitches the structure together into a three-dimensional framework where void spaces are filled by Cs+ cations. The structure of 2 contains uranium centers in UO6 tetragonal bipyramidal and UO7 pentagonal bipyramidal geometries. The uranyl moieties are bridged by phosphate anions into sinusoidal sheets that extend into the [bc] plane and are linked into a three-dimensional structure by Cu(II). The Cu centers reside in square planar environments. Charge balance is maintained by Cs+ cations. Both the overall structures and the uranyl phosphate layers in 1 and 2 are novel.     

New layered materials: syntheses, structures, and optical properties of K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiaAg(2)S(4), Cs(2)TiAg(2)sS(4), and Cs(2)TiCu(2)Se(4)

The new compounds K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiAg(2)S(4), Cs(2)TiAg(2)S(4), and Cs(2)TiCu(2)Se(4) have been synthesized by the reactions of A(2)Q(3) (A = K, Rb, Cs; Q = S, Se) with Ti, M (M = Cu or Ag), and Q at 823 K. The compounds Rb(2)TiCu(2)S(4), Cs(2)TiAg(2)S(4), and Cs(2)TiCu(2)Se(4) are isostructural. They crystallize with two formula units in space group P4(2)/mcm of the tetragonal system in cells of dimensions a = 5.6046(4) A, c = 13.154(1) A for Rb(2)TiCu(2)S(4), a =6.024(1) A, c = 13.566(4) A for Cs(2)TiAg(2)S(4), and a =5.852(2) A, c =14.234(5) A for Cs(2)TiCu(2)Se(4) at 153 K. Their structure is closely related to that of Cs(2)ZrAg(2)Te(4) and comprises [TiM(2)Q(4)(2)(-)] layers, which are separated by alkali metal atoms. The [TiM(2)Q(4)(2)(-)] layer is anti-fluorite-like with both Ti and M atoms tetrahedrally coordinated to Q atoms. Tetrahedral coordination of Ti(4+) is rare in the solid state. On the basis of unit cell and space group determinations, the compounds K(2)TiCu(2)S(4) and Rb(2)TiAg(2)S(4) are isostructural with the above compounds. The band gaps of K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiAg(2)S(4), and Cs(2)TiAg(2)S(4) are 2.04, 2.19, 2.33, and 2.44 eV, respectively, as derived from optical measurements. From band-structure calculations, the optical absorption for an A(2)TiM(2)Q(4) compound is assigned to a transition from an M d and Q p valence band (HOMO) to a Ti 3d conduction band.     

CsMBi(3)Te(6) and CsM(2)Bi(3)Te(7) (M = Pb, Sn): new thermoelectric compounds with low-dimensional structures

The new materials CsPbBi(3)Te(6) and CsPb(2)Bi(3)Te(7) were discovered through reactions of CsBi(4)Te(6) with PbTe, whereas the isostructural materials CsSnBi(3)Te(6) and CsSn(2)Bi(3)Te(7) were discovered through corresponding reactions with SnTe. The compounds can also be prepared from stoichiometric mixtures of Cs(2)Te, Pb (Sn), Bi, and Te. The crystal structures show a layered architecture of NaCl-type slabs alternating with layers of Cs atoms. This group of compounds offers a new quaternary system, Cs-M-Bi-Te (M = Pb and Sn), available for thermoelectric investigations, including fine-tuning of compositions and doping.     

Synthesis and Structure of the Layered Thorium Telluride CsTh(2)Te(6)

The compound CsTh(2)Te(6) has been synthesized at 800 degrees C by the reaction of Th with a Cs(2)Te(3)/Te melt as a reactive flux. The compound crystallizes in the space group -Cmcm of the orthorhombic system with two formula units in a cell of dimensions a = 4.367(2) ?, b = 25.119(10) ?, c = 6.140(3) ?, and V = 673.5(5) ?(3) at T = 113 K. The structure of CsTh(2)Te(6) has been determined from single-crystal X-ray data. The structure comprises infinite, two-dimensional double layers of ThTe(8)-bicapped trigonal prisms. The structural motif of the trigonal prisms resembles that found in UTe(2). Cs(+) cations, disordered equally over two crystallographically equivalent sites, separate the layers and are coordinated by eight Te atoms at the corners of a rectangular parallelepiped. Short Te-Te distances of 3.052(3) and 3.088(3) ? form linear, infinite, one-dimensional chains within the layers. Simple formalisms describe neither the Te-Te bonding in the chain nor the oxidation state of Th. The compound shows weak semiconducting behavior along the Th/Te layers perpendicular to the Te-Te chain.     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).     

Kristallstruktur von Caesiumacetat,Cs(CH3COO)

Crystal Structure of Cesium Acetate, Cs(CH₃COO) . The crystal structure of cesium acetate, Cs(CH₃COO), was determined from single crystal fourcirclediffractometer data: hexagonal crystal system, P6/m (No. 175), Z = 6, a = 1 488.0(2), c = 397.65(5) pm, V_m = 76.54(2) cm³/mol, R = 0.045, R_w = 0.030. The structure consists of flat layers of acetate anions parallel (001) that are separated by layers of cesium cations. There is a close relationship with the CaF₂ type according to CsO₂(CCH₃): each cesium cation has eight oxygen atoms as nearest neighbours. They form a heavily distorted cube with trapezoidal basal faces. In contrast to CaF₂, these polyhedra are linked via three faces and two edges to a three-dimensional network.     

Cs2Pd3(P2O7)2 and Cs2Pd3(As2O7)2: a 3D palladium phosphate with a tunnel structure and a 2D palladium arsenate containing strings of palladium atoms

Cs(2)Pd(3)(P(2)O(7))(2) (1) and Cs(2)Pd(3)(As(2)O(7))(2) (2) have been synthesized by molten flux reactions and characterized by single-crystal X-ray diffraction. The structure of 1 consists of discrete Pd(II)O(4) squares which are linked by P(2)O(7) groups via corner-sharing to generate a 3D framework containing 12-ring channels in which Cs(+) cations are located. Compound 2 adopts a 2D layer structure with the interlayer space filled with Cs(+) cations. Within a layer there are PdO(4) squares and As(2)O(7) groups fused together via corner-sharing. Adjacent layers are stacked such that strings of Pd atoms are formed. The PdO(4) squares show eclipsed and staggered stacks with alternate short and long Pd...Pd distances. The two compounds adopt considerably different structures although they have the same general formula: Cs(2)Pd(3)(X(2)O(7))(2). Compound 2 is the first palladium arsenate reported. Crystal data for 1: orthorhombic, space group Cmc2(1) (No. 36), a = 7.6061(4) A, b = 14.2820(7) A, c = 14.1840(7) A, and Z = 4. Crystal data for 2: tetragonal, space group P4/n (No. 85), a = 16.251(1) A, c = 5.9681(5) A, and Z = 4.     

Structural modulation of molybdenyl iodate architectures by alkali metal cations in AMoO3(IO3) (A = K, Rb, Cs): a facile route to new polar materials with large SHG responses

Three new molybdenyl iodates, KMoO3(IO3) (1), RbMoO3(IO3) (2), and CsMoO3(IO3) (3), have been prepared through the hydrothermal reactions of MoO3 with AIO4 (A = K, Rb, or Cs) at 180 C. These compounds are isolated as nearly colorless, air-stable crystals. Single-crystal X-ray diffraction experiments reveal that 1 possesses a corrugated layered structure constructed from molybdenum oxide chains that are bridged by iodate anions. The puckering of the layers is caused by the alignment of bent molybdenyl (MoO2(2+)) groups along one side of the molybdenum oxide chains. The K+ cations separate these layers from one another and serve to balance charge. In contrast, compounds 2 and 3, which are isostructural, form three-dimensional structures with small cavities filled with Rb+ or Cs+ cations. The differences between the structures of 1 and those of 2 and 3 are due to rotation of the molybdenyl units as translation occurs down the molybdenum oxide chains in order to accommodate the increased size of the Rb+ and Cs+ cations. This rotation allows for the iodate anions to bridge the molybdenum oxide chains in an additional dimension, creating a three-dimensional network structure. Furthermore, while 1 crystallizes in a centrosymmetric space group, 2 and 3 crystallize in polar space groups. Second-harmonic generation measurements on 2 and 3 show large responses of 400x alpha-quartz. Differential scanning calorimetry measurements demonstrate that 2 and 3 are thermally stable to 494 and 486 C, respectively. UV-vis diffuse reflectance spectra of these compounds show a high degree of transparency from 1 to 3 eV and a band gap of 3.1 eV.     

New Layered Polyborates Cs(2)M(2)B(10)O(17) (M = Na, K)

The polyborates Cs(2)M(2)B(10)O(17) (M = Na, K) have been prepared and their structures determined by single-crystal X-ray diffraction methods. They crystallize in the monoclinic space group C2/c (Z = 8) with unit-cell parameters a = 21.643(3) ?, b = 6.558(2) ?, c = 11.072(2) ?, beta = 105.43(1) degrees, V = 1514.8(6) ?(3) for the Na compound and a = 22.547(9) ?, b = 6.614(2) ?, c = 11.288(4) ?, beta = 103.25 degrees, V = 1638.3(8) ?(3) for the K analogue. The new structural type contains a 2-dimensional borate matrix that is built from a complete condensation of the ring system B(5)O(11). The Cs atoms reside within the borate matrix, and the Na (K) atoms are placed between the thick Cs borate sheets.     

Synthesis and characterization of Mo(6) chalcobromides and cyano-substituted compounds built from a novel [(Mo(6)Br(i)(6)Y(i)(2))L(a)(6)](n)()(-) discrete cluster unit (Y(i) = S or Se and L(a) = Br or CN)

The syntheses, crystal structures determined by single-crystal X-ray diffraction, and characterizations of new Mo(6) cluster chalcobromides and cyano-substituted compounds with 24 valence electrons per Mo(6) cluster (VEC = 24), are presented in this work. The structures of Cs(4)Mo(6)Br(12)S(2) and Cs(4)Mo(6)Br(12)Se(2) prepared by solid state routes are based on the novel [(Mo(6)Br(i)(6)Y(i)(2))Br(a)(6)](4)(-) (Y = S, Se) discrete units in which two chalcogen and six bromine ligands randomly occupy the inner positions, while the six apical ones are fully occupied by bromine atoms. The interaction of these two compounds with aqueous KCN solution results in apical ligand exchange giving the two first Mo(6) cyano-chalcohalides: Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)S(2))(CN)(6)](3).16H(2)O and Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)Se(2))(CN)(6)](3).16H(2)O. Their crystal structures, built from the original [(Mo(6)Br(i)(6)Y(i)(2))(CN)(a)(6)](4)(-) discrete units, will be compared to those of the two solid state precursors and other previously reported Mo(6) cluster compounds. Their redox properties and (77)Se NMR characterizations will be presented. Crystal data: Cs(4)Mo(6)Br(12)S(2), orthorhombic, Pbca (No. 61), a = 11.511(5) A, b = 18.772(5) A, c = 28.381 A (5), Z = 8; Cs(4)Mo(6)Br(12)Se(2), Pbca (No. 61), a = 11.6237(1) A, b = 18.9447(1) A, c = 28.4874(1) A, Z = 8; Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)S(2))(CN)(6)](3).16H(2)O, Pm-3m (No. 221), a = 17.1969(4) A, Z = 1; Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)Se(2))(CN)(6)](3).16H(2)O, Pm-3m (No. 221), a = 17.235(5) A, Z = 1.     

Structural chemistry of "defect" cyanometalate boxes: (Cs subset [CpCo(CN)3]4[Cp*Ru]3) and (M subset [Cp*Rh(CN)3]4[Cp*Ru]3) (M = NH4, Cs)

A series of heptametallic cyanide cages are described; they represent soluble analogues of defect-containing cyanometalate solid-state polymers. Reaction of 0.75 equiv of [Cp*Ru(NCMe)3]PF6, Et(4)N[Cp*Rh(CN)3], and 0.25 equiv of CsOTf in MeCN solution produced (Cs subset [CpCo(CN)3]4[Cp*Ru]3)(Cs subset Rh4Ru3). 1H and 133Cs NMR measurements show that Cs subset Rh4Ru3 exists as a single Cs isomer. In contrast, (Cs subset [CpCo(CN)3]4[Cp*Ru]3) (Cs subset Co4Ru3), previously lacking crystallographic characterization, adopts both Cs isomers in solution. In situ ESI-MS studies on the synthesis of Cs subset Rh4Ru3 revealed two Cs-containing intermediates, Cs subset Rh2Ru2+ (1239 m/z) and Cs subset Rh3Ru3+ (1791 m/z), which underscore the participation of Cs+ in the mechanism of cage formation. 133Cs NMR shifts for the cages correlated with the number of CN groups bound to Cs+: Cs subset Co4Ru4+ (delta 1 vs delta 34 for CsOTf), Cs subset Rh4Ru3 where Cs+ is surrounded by ten CN ligands (delta 91), Cs subset Co4Ru3, which consists of isomers with 11 and 10 pi-bonded CNs (delta 42 and delta 89, respectively). Although (K subset [Cp*Rh(CN)3]4[Cp*Ru]3) could not be prepared, (NH4 subset [Cp*Rh(CN)3]4[Cp*Ru]3) (NH4 subset Rh4Ru3) forms readily by NH4+-template cage assembly. IR and NMR measurements indicate that NH4+ binding is weak and that the site symmetry is low. CsOTf quantitatively and rapidly converts NH4 subset Rh4Ru3 into Cs subset Rh4Ru3, demonstrating the kinetic advantages of the M7 cages as ion receptors. Crystallographic characterization of CsCo4Ru3 revealed that it crystallizes in the Cs-(exo)1(endo)2 isomer. In addition to the nine mu-CN ligands, two CN(t) ligands are pi-bonded to Cs+. M subset Rh4Ru3 (M = NH4, Cs) crystallizes as the second Cs isomer, that is, (exo)2(endo)1, wherein only one CN(t) ligand interacts with the included cation. The distorted framework of NH4 subset Rh4Ru3 reflects the smaller ionic radius of NH4+. The protons of NH4+ were located crystallographically, allowing precise determination of the novel NH4...CN interaction. A competition experiment between calix[4]arene-bis(benzocrown-6) and NH4 subset Rh4Ru3 reveals NH4 subset Rh4Ru3 has a higher affinity for cesium.     

Quaternary tellurides with different valent Ge centers: Cs2Ge3M6Te14 (M = Ga, In)

New quaternary tellurides, Cs(2)Ge(3)M(6)Te(14) (M = Ga, In), were discovered by solid-state reactions. These compounds crystallize in space group P3ml (No. 164), with a = b = 8.2475(2) ?, c = 14.2734(8) ?, and V = 840.82(6) ?(3) (Z = 1) for Cs(2)Ge(3)Ga(6)Te(14) (1) and a = b = 8.5404(2) ?, c = 14.6766(8) ?, and V = 927.07(6) ?(3) (Z = 1) for Cs(2)Ge(3)In(6)Te(14) (2). The remarkable structural feature is the novel three-dimensional [Ge(3)M(6)Te(14)](2-) anionic framework made by condensed In(6)Te(14) (or Ga(6)Te(14)) layers that are connected alternately by dimeric Ge(3+)(2)Te(6) units and Ge(2+)Te(6) octahedra along the c direction. The presence of Ge centers with different oxidation states is also supported by the results of the electron localization function calculation and X-ray photoelectron spectroscopy measurement.     

Hydrothermal synthesis and structure of a new one-dimensional, mixed-metal U(VI) iodate, Cs(2)[(UO(2))(CrO(4))(IO(3))(2)

The reaction of the molecular transition metal iodate, Cs[CrO(3)(IO(3))], with UO(3) under mild hydrothermal conditions provides access to a new low-dimensional, mixed-metal U(VI) compound, Cs(2)[(UO(2))(CrO(4))(IO(3))(2)] (1). The structure of 1 is quite unusual and consists of one-dimensional (1)(infinity)[(UO(2))(CrO(4))(IO(3))(2)](2-) ribbons separated by Cs(+) cations. These ribbons are formed from [UO(7)] pentagonal bipyramids that contain a uranyl core, [CrO(4)] tetrahedra, and both monodentate and bridging iodate anions. Crystallographic data: 1, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4 (T = 193 K).     

Ln(terpy)]3+ (Ln = Sm, Gd) entity forms isolated magnetic chains with [W(CN)8]3-

The reaction between Ln(NO3)3*xH2O, Cs3[W(V)(CN)8]*H2O and 2,2':6',2'-terpyridine (terpy) leads to the original isomorphous cyano-bridged [Ln(III)(terpy)(DMF)4][W(V)(CN)8] *6H2O [Ln = Gd (1), Sm (2)] 1-D chains. The crystal structures of {Ln(III)W(V)} chains and consist of alternating {[W(CN)8]} and {[Ln(terpy)]} building blocks. The neighbouring 1-D chains are weakly linked through pi-pi stacking interactions of the aromatic rings leading to 2-D supramolecular layers. The layers are linked through hydrogen bonds between H2O molecules and terminal cyano ligands. Magnetic studies revealed a weak antiferromagnetic coupling (J = -2.3(2) K) within the {Gd(III)W(V)} chains in . The positive effective coupling constant J = +2.0(5) K between the total angular momentum of the Sm(III) centre and the spin of the W(v) ion is equivalent to an antiferromagnetic character of the spin coupling between both centres in the {Sm(III)W(V)} chains of 2. The magnetic measurements suggest that they display an isolated magnetic chain behaviour.     

The ball-shaped heteropolytungstates [[Sn(CH3)2(H2O)]24[Sn(CH3)2]12(A-XW9O34)12]36- (X=P, As): stability, redox and electrocatalytic properties in aqueous media

The electrochemical behavior of the ball-shaped heteropolytungstates [[Sn(CH(3))(2)(H(2)O)](24)[Sn(CH(3))(2)](12)(A-XW(9)O(34))(12)](36-) (X=P, 1; As, 2) was examined in aqueous electrolytes by redissolution of their respective mixed cesium-sodium salts Cs(14)Na(22)[[Sn(CH(3))(2)(H(2)O)](24)[Sn(CH(3))(2)](12) (A-PW(9)O(34))(12)]149 H(2)O (Cs(14)-1) and Cs(14)Na(22)[[Sn(CH(3))(2)(H(2)O)](24)[Sn(CH(3))(2)](12)(A-AsW(9)O(34))(12)]149 H(2)O (Cs(14)-2). In the studied media, Cs(14)-2 is readily soluble in contrast to the significantly less soluble Cs(14)-1. The solubility of Cs(14)-1 is increased by the presence of Li(+) ions in solution. Gel filtration studies with 1 and 2 rule out a decay of the dodecameric spherical assemblies to Keggin-based monomers on the timescale of the experiment. By UV/Vis spectroscopy and cyclic voltammetry, 2 was found to be significantly less stable than 1 and both polyanions also show rather different decomposition pathways. Polyanion 1 collapses first into Keggin-type monomers which might contain the trilacunary [A-alpha-PW(9)O(34)](9-). The final monomeric species obtained from 1 appears to be very similar to [PW(11)O(39)](7-), which is the final transformation product of [A-alpha-PW(9)O(34)](9-) in the same media. In contrast, 2 does not seem to follow an analogous transformation pathway as that of the trilacunary [A-alpha-AsW(9)O(34)](9-). Importantly, stabilization of 1 is observed in chloride media. The fairly long-term stability of 1 in 1 M LiCl, pH 3, has allowed for its electrochemical study to be carried out. The solid-state cyclic voltammogram of 1 entrapped in a carbon paste electrode shows the same characteristics as 1 dissolved in chloride solutions, thus supporting the conclusion that the polyanion is stable in these environments. Controlled potential coulometry on 1 indicates that the number of electrons consumed in the first wave is larger than twenty. To our knowledge, 1 constitutes the first example of a molecule that can take up such a large number of electrons resulting in a chemically reversible W-wave. These properties show promise for future fundamental and applied studies. Polyanion 1 is also efficient in the electrocatalytic reduction of NO(x), including nitrate. Finally, a remarkable interaction was found between 1 and NO, a highly promising feature for biomimetic applications.     

Isolation and characterization of carbene derivatives of La@C82(Cs)

The photochemical reaction of La@C82(Cs) with 2-adamantane-2,3-[3H]-diazirine (1) affords the adduct 2 of La@C82(Cs) with adamantylidene (Ad:) in a high selectivity. The two isomers of La@C82(Cs)(Ad), 2a and 2b, are isolated by HPLC and characterized by electron spin resonance, mass, and UV-vis-near-infrared spectroscopies. The electronic properties of 2a and 2b are very similar to that of the pristine La@C82(Cs), suggesting that 2a and 2b retain the essential electronic and structural character of La@C82(Cs).     

Hydrothermal synthesis and characterization of new pillared layered ethylenediphosphonates of molybdenum(VI), A2[Mo2O5(O3PCH2CH2PO3)] (A = NH4, Tl, Cs, Rb) and K(H3O)[Mo2O5(O3PCH2CH2PO3)

New ethylenediphosphonates of molybdenum, A[Mo2O5(O3PCH2CH2PO3)] (A = NH4 (1), Tl (2), Cs (3), Rb (4)), and K(H3O)[Mo2O5(O3PCH2CH2PO3)] (5), have been synthesized by a hydrothermal method and structurally characterized by X-ray diffraction, spectroscopic, and thermal studies. These compounds consist of pillared anionic layers [Mo2O5(O3PCH2CH2PO3)]2-, with A+, K+, and H3O+ ions in the interlayer region as well as in the cavities within the anionic layers. Single-crystal X-ray structures of compounds 1 and 5 have been determined. They crystallize in the orthorhombic space group Cmca with Z = 8 and have the following unit cell parameters. For 1, a = 25.60(1), b = 10.016(4), and c = 9.635(3) angstroms and for 5, a = 25.63(1), b = 10.007(2), and c = 9.512(1) angstroms.     

Rb(3)Ti(3)(P(4)S(13))(PS(4))(3) and Cs(2)Ti(2)(P(2)S(8))(PS(4))(2): two polar titanium thiophosphates with complex one-dimensional tunnels

The reactions of Ti with in situ formed polythiophosphate fluxes of A(2)S(3) (A = Rb, Cs), P(2)S(5), and S at 500 degrees C result in the formation of two new quaternary titanium thiophosphates with compositions Rb(3)Ti(3)(P(4)S(13))(PS(4))(3) (1) and Cs(2)Ti(2)(P(2)S(8))(PS(4))(2) (2). Rb(3)Ti(3)(P(4)S(13))(PS(4))(3) (1) crystallizes in the chiral hexagonal space group P6(3) (No. 173) with lattice parameters a = 18.2475(9) Angstrom, c = 6.8687(3) Angstrom, V = 1980.7(2) Angstrom(3), Z = 2. Cs(2)Ti(2)(P(2)S(8))(PS(4))(2) (2) crystallizes in the noncentrosymmetric monoclinic space group Cc (No. 9) with a = 21.9709(14) Angstrom, b = 6.9093(3) Angstrom, c = 17.1489(10) Angstrom, beta = 98.79(1) degrees, V = 2572.7(2) Angstrom(3), Z = 4. In the structure of 1 TiS(6) octahedra, three [PS(4)] tetrahedra, and the hitherto unknown [P(4)S(13)](6-) anion are joined to form two different types of helical chains. These chains are connected yielding two different helical tunnels being directed along [001]. The tunnels are occupied by the Rb+ ions. The [P(4)S(13)](6-) anion is generated by three [PS(4)] tetrahedra sharing corners with one [PS(4)] group in the center of the starlike anion. The P atoms of the three [PS(4)] tetrahedra attached to the central [PS(4)] group define an equilateral triangle. The [P(4)S(13)](6-) anion may be regarded as a new member of the [P(n)S(3n+1)]((n+2)-) series. The structure of Cs(2)Ti(2)(P(2)S(8))(PS(4))(2) (2) consists of the one-dimensional polar tunnels containing the Cs(+) cations. The rare [P(2)S(8)](4-) anion which is composed of two [PS(4)] tetrahedra joined by a S(2)(2-) anion is a fundamental building unit in the structure of 2. One-dimensional undulated chains being directed along [100] are joined by [PS(4)] tetrahedra to form the three-dimensional network with polar tunnels running along [010]. The compounds are characterized with IR, Raman spectroscopy, and UV/vis diffuse reflectance spectroscopy.     

Synthesis, structure, and properties of Cs(4)Th(4)P(4)Se(26): a quaternary thorium selenophosphate containing the (P(2)Se(9))(6-) anion

Orange crystals of Cs(4)Th(4)P(4)Se(26) were grown from the reaction of (232)Th and P in a Cs(2)Se(3)/Se molten salt flux at 750 degrees C. Cs(4)Th(4)P(4)Se(26) crystallizes in the orthorhombic space group Pbca with the unit cell parameters: a = 12.0130(6), b = 14.5747(7), c = 27.134(1) A; Z = 8. The compound exhibits a three-dimensional structure, consisting of dimeric [Th(2)Se(13)] polyhedral units. The two crystallographically independent, nine-coordinate, bicapped trigonal prismatic thorium atoms share a triangular face to form the dimer, and each dimer edge-shares two selenium atoms with two other dimers to form kinked chains along the [010] direction. While this structure shares features of the previously reported Rb(4)U(4)P(4)Se(26), including phosphorus in the 5+ oxidation state, careful inspection of the structure reveals that the selenophosphate anion that knits the structure together in three directions in both compounds is a unique (P(2)Se(9))(6-) anion. The formula may be described best as [Cs(2)Th(2)(P(2)Se(9))(Se(2))(2)](2). The (P(2)Se(9))(6-) anion features a nearly linear Se-Se-Se backbone with an angle of 171 degrees and Se-Se distances that are approximately 0.2-0.3 A longer than the typical single Se-Se bond. Magnetic studies confirm that this phase contains Th(IV). Raman data for this compound is reported, and structural comparisons will be drawn to its uranium analogue, Rb(4)U(4)P(4)Se(26).     

碱金属硒化物MHgSbSe~3(M=K,Rb, Cs)的晶体结构及其半导体性 质的研究

用有机溶剂热生长技术(SolvothermalTechnique)制备碱金属硒化物MHgSbSe~3(M=K,Rb,Cs),用单晶X射线衍射技术对其进行晶体结构分析,热分析结果表明,在常温(<200℃)下均为稳定的化合物。光学性质测试表明它们是半导体材料,KHgSbSe~3,RbHgSbSe~3,CsHgSbSe~3的禁带宽度依次为1.85eV,1.75eV,1.65eV。