Organoruthenium derivative of the cyclic [H7P8W48O184]33- anion: [{K(H2O)}3{Ru(p-cymene)(H2O)}4P8W49O186(H2O)2]27-

Reaction of [Ru(p-cymene)Cl2]2 with [H7P8W48O184]33- (P8W48) in aqueous acidic medium results in the organometallic derivative [{K(H2O)}3{Ru(p-cymene)(H2O)}4P8W49O186(H2O)2]27- (1); in addition to the four {Ru(p-cymene)(H2O)} units, an unusual WO6 group with four equatorial, terminal ligands is also grafted to the crown-shaped P8W48 precursor.     

Synthesis, crystal structure from single-crystal and powder X-ray diffraction data, and thermal behavior of mixed potassium lanthanide squarates: thermal transformations of layered [Ln(H2O)6]K(H2C4O4)(C4O4)2 into pillared LnK(C4O4)2 (Ln = Y, La, Gd, Er)

A new series of mixed potassium and rare-earth squarates, [Ln(H(2)O)(6)]K(H(2)C(4)O(4))(C(4)O(4))(2) (Ln = Y, La, Gd, Er), has been synthesized and structurally characterized from single-crystal X-ray diffraction and spectroscopic analyses. The yttrium-based compound crystallizes with a monoclinic symmetry, space group C2/c [a = 8.3341(2) A, b = 37.7094(9) A, c = 11.7195(3) A, beta = 90.3959(9) degrees , V = 3683.1(2) A(3), Z = 8]. The structure is built from layers maintained together via hydrogen bonds. Within a layer, squarate ligands act as linkers between lanthanide and potassium cations. The thermal decomposition of the precursors has been studied by powder thermodiffractometry and thermal analyses. It is shown that crystalline intermediate phases are formed during the degradation. Among them, unprecedented mixed anhydrous squarates, LnK(C(4)O(4))(2), could be isolated. The crystal structure of the Y compound has been solved ab initio from X-ray powder diffraction data, using direct-space methods [a = 6.2010(5) A, c = 11.639(1) A, V = 447.55 A(3), Z = 2]. The structure consists of layers of edge-sharing YO(8) and KO(8) antiprisms, pillared by mu(8)-squarate groups. The end of the precursor decomposition is marked by the formation of cubic sesquioxides Ln(2)O(3), including lanthanum oxide.     

Nucleation process in the cavity of a 48-tungstophosphate wheel resulting in a 16-metal-centre iron oxide nanocluster

The 16-Fe(III)-containing 48-tungsto-8-phosphate [P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)](20-) (1) has been synthesised and characterised by IR and ESR spectroscopy, TGA, elemental analyses, electrochemistry and susceptibility measurements. Single-crystal X-ray analyses were carried out on Li(4)K(16)[P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)]66 H(2)O2 KCl (LiK-1, orthorhombic space group Pnnm, a=36.3777(9) A, b=13.9708(3) A, c=26.9140(7) A, and Z=2) and on the corresponding mixed sodium-potassium salt Na(9)K(11)[P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)].100 H(2)O (NaK-1, monoclinic space group C2/c, a=46.552(4) A, b=20.8239(18) A, c=27.826(2) A, beta=97.141(2) degrees and Z=4). Polyanion 1 contains--in the form of a cyclic arrangement--the unprecedented {Fe(16)(OH)(28)(H(2)O)(4)}(20+) nanocluster, with 16 edge- and corner-sharing FeO(6) octahedra, grafted on the inner surface of the crown-shaped [H(7)P(8)W(48)O(184)](33-) (P(8)W(48)) precursor. The synthesis of 1 was accomplished by reaction of different iron species containing Fe(II) (in presence of O(2)) or Fe(III) ions with the P(8)W(48) anion in aqueous, acidic medium (pH approximately 4), which can be regarded as an assembly process under confined geometries. One fascinating aspect is the possibility to model the uptake and release of iron in ferritin. The electrochemical study of 1, which is stable from pH 1 through 7, offers an interesting example of a highly iron-rich cluster. The reduction wave associated with the Fe(III) centres could not be split in distinct steps independent of the potential scan rate from 2 to 1000 mV s(-1); this is in full agreement with the structure showing that all 16 iron centres are equivalent. Polyanion 1 proved to be efficient for the electrocatalytic reduction of NO(x), including nitrate. Magnetic and variable frequency EPR measurements on 1 suggest that the Fe(III) ions are strongly antiferromagnetically coupled and that the ground state is tentatively spin S=2.     

Polyoxometalate (W/Mo) compounds connected via lanthanide cations with a three-dimensional framework, H2{[K(H2O)2]2[Ln(H2O)5]2(H2M12O42)}.nH2O: synthesis, structures, and magnetic properties

A series of 10 novel polyoxometalate (W/Mo) compounds connected via a trivalent lanthanide cation bridge, H2{[K(H2O)2]2[Ln(H2O)5]2(H2M12O42)}.n(H2O) (Ln = La, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu; M = W or W/Mo) (1-10), were designed and synthesized on the basis of the abduction of Al3+ in aqueous solution. X-ray diffraction analyses reveal that the structures of complexes 1-10 are three-dimensional frameworks assembled from the arrangement of H2M12O42(10-) (named paradodecmetalate-B) and Ln(H2O)53+ with two planes, which are constructed via the unification of H2M12O42(10-) and Ln(H2O)53+, along the [100] and [001] directions. Magnetic measurements reveal the paramagnetic properties and a strong ferromagnetic coupling between the two nearest-neighboring lanthanide cations, Ln3+ (Ln = Dy, Er), within the circle for compounds 2 and 4-9.     

Syntheses,structures, and properties of the bis(cyclopentadienyl) rare-earth imidodiphosphinochalocogenido compounds Cp2Ln[N(QPPh2)2] (Ln = La,Gd, Er,or Yb for Q = Se; Ln = Yb for Q = S)

The compounds Cp2Ln[N(QPPh2)2] (Ln = La (1), Gd (2), Er (3), or Yb (4) for Q = Se, Ln = Yb (5) for Q = S) have been synthesized from the corresponding rare-earth tris(cyclopentadienyl) compound and H[N(QPPh2)2]. The structures of compounds 1, 2, 3, and 5, as determined by X-ray crystallography, consist of a Cp2Ln fragment, coordinated eta 3 through two chalcogen atoms and an N atom of the imidodiphosphinochalcogenido ligand [N(QPPh2)2]-. In compound 4, the Cp2Yb moiety is coordinated eta 2 through the two Se atoms of the [N(SePPh2)2]-ligand. 31P and 77Se (for 1) NMR spectroscopies lend insight into the solution nature of these species. Crystal data: 1, C34H30LaNP2Se2, triclinic, P1, a = 9.7959(10) A, b = 12.4134(13) A, c = 13.9077(14) A, alpha = 88.106(2) degrees, beta = 88.327(2) degrees, gamma = 68.481(2) degrees, V = 1572.2(3) A3, T = 153 K, Z = 2, and R1(F) = 0.0257 for the 5947 reflections with I > .2 sigma(I); 2, C34H30GdNP2Se2, triclinic, P1, a = 9.7130(14) A, b = 12.2659(17) A, c = 13.953(2) A, alpha = 88.062(2) degrees, beta = 87.613(2) degrees, gamma = 69.041(2) degrees, V = 1550.7(4) A3, T = 153 K, Z = 2, and R1(F) = 0.0323 for the 5064 reflections with I > 2 sigma(I); 3, C34H30ErNP2Se2, triclinic, P1, a = 9.704(2) A, b = 12.222(3) A, c = 13.980(4) A, alpha = 88.230(4) degrees, beta = 87.487(4) degees, gamma = 69.107(4) degrees, V = 1547.4(7) A3, T = 153 K, Z = 2, and R1(F) = 0.0278 for the 6377 reflections with I > 2 sigma(I); 4, C34H30NP2Se2Yb.C4H8O, triclinic, P1, a = 12.087(4) A, b = 12.429(4) A, c = 23.990(7) A, alpha = 89.406(5) degrees, beta = 86.368(5) degrees, gamma = 81.664(5) degrees, V = 3558.8(18) A3, T = 153 K, Z = 4, and R1(F) = 0.0321 for the 11,883 reflections with I > 2 sigma(I); and 5, C34H30NP2S2Yb, monoclinic, P21/n, a = 13.8799(18) A, b = 12.6747(16) A, c = 17.180(2) A, beta = 91.102(3) degrees, V = 3021.8(7) A3, T = 153 K, Z = 4, and R1(F) = 0.0218 for the 6698 reflections with I > 2 sigma(I).     

新型三维开放骨架稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4(Ln=Gd,Eu)的合成、结构及荧光性质

以哌嗪为模板剂,在水-乙醇混合溶剂体系中溶剂热合成了两个具有三维开放骨架结构的稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4（Ln = Gd,化合物1和Eu,化合物2）,并对其进行了结构表征、热重以及荧光光谱分析. 单晶结构解析表明,化合物1和2属于同构异质,均结晶于单斜晶系,P21/c空间群,化合物1,a = 19.691(3) ?,b = 19.249(3) ?,c = 13.186(2) ?,β = 92.33(0)o,V = 4993.5(1) ?3, Z =4. 化合物2,a = 19.7233(8) ?,b = 19.2791(8) ?,c = 13.2095(5) ?,β = 92.329(1)o,V = 5018.7(3) ?3, Z =4. 两个化合物在ab平面上由SO4,GdO8和GdO9多面体共边或共角交错连接形成含有八元环和十六元环的二维层状结构,该二维层沿c方向平行排列,相邻层通过SO4四面体相连形成具有孔道的三维开放骨架结构,其孔道之中包含平衡骨架负电荷的质子化哌嗪分子. 化合物2的固体荧光光谱分析显示其在397nm激发波长下,表现出典型的Eu3+发光性质.       

Two new groups of homoleptic rare earth pyridylbenzimidazolates: (NC12H8(NH)2)[Ln(N3C12H8)4] with Ln = Y,Tb, Yb,and [Ln(N3C12H8)2(N3C12H9)2][Ln(N3C12H8)4](N3C12H9)2 with Ln = La,Sm, Eu

The compounds (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y, Tb, Yb, and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), with Ln = La, Sm, Eu, were obtained by reactions of the group 3 metals yttrium and lanthanum as well as the lanthanides europium, samarium, terbium, and ytterbium with 2-(2-pyridyl)-benzimidazole. The reactions were carried out in melts of the amine without any solvent and led to two new groups of homoleptic rare earth pyridylbenzimidazolates. The trivalent rare earth atoms have an eightfold nitrogen coordination of four chelating pyridylbenzimidazolates giving an ionic structure with either pyridylbenzimidazolium or [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)](+) counterions. With Y, Eu, Sm, and Yb, single crystals were obtained whereas the La- and Tb-containing compounds were identified by powder methods. The products were investigated by X-ray single crystal or powder diffraction and MIR and far-IR spectroscopy, and with DTA/TG regarding their thermal behavior. They are another good proof of the value of solid-state reaction methods for the formation of homoleptic pnicogenides of the lanthanides. Despite their difference in the chemical formula, both types (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y (1), Tb (2), Yb (3), and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), Ln = La (4), Sm (5), Eu (6), crystallize isotypic in the tetragonal space group I4(1). Crystal data for (1): T = 170(2) K, a = 1684.9(1) pm, c = 3735.0(3) pm, V = 10603.5(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.053, wR2 = 0.113. Crystal data for (3): T = 170(2) K, a = 1683.03(7) pm, c = 3724.3(2) pm, V = 10549.4(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.047, wR2 = 0.129. Crystal data for (5): T = 103(2) K, a = 1690.1(2) pm, c = 3759.5(4) pm, V = 10739(2) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.050, wR2 = 0.117. Crystal data for (6): T = 170(2) K, a = 1685.89(9) pm, c = 3760.0(3) pm, V = 10686.9(11) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.060, wR2 = 0.144.     

Anion-directed crystallization of coordination polymers: syntheses and characterization of Cu(4)(2-pzc)(4)(H(2)O)(8)(Mo(8)O(26)).2H(2)O and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2-pzc = 2-pyrazinecarboxylate)

Two new copper 2-pyrazinecarboxylate (2-pzc) coordination polymers incorporating [Mo(8)O(26)](4-) and [V(10)O(28)H(4)](2-) anions were synthesized and structurally characterized: Cu(4)(2-pzc)(4))(H(2)O)(8)(Mo(8)O(26)).2H(2)O (1) and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2). Crystal data: 1, monoclinic, space group P2(1)/n, a = 11.1547(5) A, b = 13.4149(6) A, c = 15.9633(7) A, beta = 90.816(1) degrees; 2, triclinic, space group P1, a = 10.5896(10) A, b = 10.7921(10) A, c = 13.5168(13) A, alpha = 104.689(2) degrees, beta = 99.103(2) degrees, gamma = 113.419(2) degrees. Compound 1 contains [Cu(2-pzc)(H(2)O)(2)] chains charge-balanced by [Mo(8)O(26)](4-) anions. In compound 2, layers of [Cu(3)(2-pzc)(4)(H(2)O)(2)] form cavities that are filled with [V(10)O(28)H(4)](2-) anions. The magnetic properties of both compounds are described.     

Structure,magnetism, and electrochemistry of the multinickel polyoxoanions [Ni6As3W24O94(H2O)2]17-, [Ni3Na(H2O)2(AsW9O34)2]11-, and [Ni4Mn2P3W24O94(H2O)2]17-

The three novel, multi-nickel-substituted heteropolytungstates [Ni(6)As(3)W(24)O(94)(H(2)O)(2)](17)(-) (1), [Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)](11)(-) (2), and [Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)](17)(-) (3) have been synthesized and characterized by IR, elemental analysis, electrochemistry, and magnetic studies. Single-crystal X-ray analysis was carried out on Na(16.5)Ni(0.25)[Ni(6)As(3)W(24)O(94)(H(2)O)(2)].54H(2)O, which crystallizes in the triclinic system, space group P1, with a = 17.450(4) A, b = 17.476(4) A, c = 22.232(4) A, alpha = 85.73(3) degrees, beta = 89.74(3) degrees, gamma = 84.33(3) degrees, and Z = 2, Na(11)[Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)].30.5H(2)O, which crystallizes in the triclinic system, space group P1, with a = 12.228(2) A, b = 16.743(3) A, c = 23.342(5) A, alpha = 78.50(3) degrees, beta = 80.69(3) degrees, gamma = 78.66(3) degrees, and Z = 2, and Na(17)[Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)].50.5H(2)O, which crystallizes in the monoclinic system, space group P2(1)/c, with a = 17.540(4) A, b = 22.303(5) A, c = 35.067(7) A, beta = 95.87(3) A, and Z = 4. Polyanion 1 consists of two B-alpha-(Ni(3)AsW(9)O(40)) Keggin moieties linked via a unique AsW(6)O(16) fragment, leading to a banana-shaped structure with C(2)(v)() symmetry. The mixed-metal tungstophosphate 3 is isostructural with 1. Polyanion 2 consists of two lacunary B-alpha-[AsW(9)O(34)](9)(-) Keggin moieties linked via three nickel(II) centers and a sodium ion. Electrochemical studies show that 1-3 exhibit a unique and reproducible voltammetric pattern and that all three compounds are stable in a large pH range. An investigation of the magnetic properties of 1-3 indicates that the exchange interactions within the trimetal clusters are ferromagnetic. However, for 1 and 3 intra- and intermolecular interactions between different trinuclear clusters are also present.     

Cluster-type basic lanthanide iodides [M6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 (M = Nd, Eu, Tb, Dy)

Ln6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)(8) (Ln = Nd, Eu, Tb, Dy) compounds are obtained as the final hydrolysis products of lanthanide triiodides in an aqueous solution. Their X-ray crystal structure features a body-centered arrangement of oxygen-centered {Ln6X8}8+ cluster cores: [Nd6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1310.4(3) pm, b = 1502.1(3) pm, c = 1514.9(3) pm, 3384 reflections with I0 > 2sigma(I0), R1 = 0.0340, wR2 = 0.0764, GOF = 1.022, T = 298(2) K], [Eu6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1306.6(2) pm, b = 1498.15(19) pm, c = 1499.41(18) pm, 4262 reflections with I0 > 2sigma(I0), R1 = 0.0540, wR2 = 0.0860, GOF = 0.910, T = 298(2) K], [Tb6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 4182 reflections with I0 > 2sigma(I0), R1 = 0.0395, wR2 = 0.0924, GOF = 1.000, T = 298(2) K], and [Dy6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 3329 reflections with I0 > 2sigma(I0), R1 = 0.0389, wR2 = 0.0801, GOF = 0.992, T = 298(2) K.     

Two wheel-like polytungstates obtained by incorporation of two {Cu(4)} clusters and two molybdenum centers in the {W(48)} wheel

Two new {P(8)W(48)} wheel-based compounds, Na(12)Li(16){[Cu(H(2)O)](2)[Cu(4)(OH)(4)(H(2)O)(8)](2)P(8)W(48)O(184)}·55H(2)O (1), and K(4)Na(24)Li(10){(MoO(2))(2)(P(8)W(48)O(184))}·61H(2)O (2) have been synthesized by a conventional aqueous solution method, and characterized by UV, IR, TG analysis, XPRD, (31)P NMR, XPS, single-crystal X-ray diffraction analyses, magnetic study and electrochemistry study. In compound 1, a wheel-type {P(8)W(48)} containing two {Cu(4)} clusters and two isolated Cu cations results in a 10-Cu-containing polyoxotungstate, which represents the first {P(8)W(48)}-based compound trapping two transition metal (TM) clusters in its inner cavity. Further, the polyoxoanion was connected by Na(+) and Li(+) cations into a 3D framework. Compound 2 is a 2-Mo-containing {P(8)W(48)}-based polyoxotungstate. Magnetic study indicates that antiferromagnetic interactions exist in compound 1.     

Sandwich-type silicotungstates: structure and magnetic properties of the dimeric polyoxoanions[[SiM2W9O34(H2O)]2]12- (M = Mn2+, Cu2+, Zn2+)

The novel dimeric silicotungstates [[SiM2W9O34(H2O)]2]12- (M = Mn2+, Cu2+, Zn2+) have been synthesized and characterized by IR spectroscopy, elemental analysis, and magnetic measurements. X-ray single-crystal analyses were carried out on K4Na6Mn[[SiMn2W9O34(H2O)]2].33H2O (1), which crystallizes in the triclinic system, space group P1, with a = 12.2376(7) A, b = 13.6764(8) A, c = 15.6177(9) A, alpha = 70.2860(10) degrees, beta = 79.9150(10) degrees, gamma = 70.2760(10) degrees, and Z = 1; K3Na5[[SiCu2W9O34(H2O)]2].26H2O (2) crystallizes in the triclinic system, space group P1, with a = 11.4271(12) A, b = 12.5956(13) A, c = 15.3223(16) A, alpha = 80.456(2)degrees, beta = 76.383(2) degrees, gamma = 76.968(2) degrees, and Z = 1; K4Na6[[SiZn2W9O34(H2O)]2].34H2O (3) crystallizes also in the triclinic system, space group P1, with a = 12.2596(14) A, b = 13.2555(15) A, c = 16.2892(18) A, alpha = 96.431(2) degrees, beta = 100.944(2) degrees, gamma = 110.404(2) degrees, and Z = 1. The polyanions consist of two lacunary B-alpha-[SiW9O34]10- Keggin moieties linked via a rhomblike M4O16 (M = Mn, Cu, Zn) group leading to a sandwich-type structure. Magnetic measurements show that the central Mn4 unit in 1 exhibits antiferromagnetic (J = -1.77(5) cm(-1)) as well as weak ferromagnetic (J' = 0.08(2) cm(-1)) Mn-Mn exchange interactions. In 2 the Cu-Cu exchange interactions are antiferromagnetic (J = -0.10(2) cm(-1), J' = -0.29(2) cm(-1)).     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Extended polyoxometalate framework solids: two Mn(II)-linked {P8W48} network arrays

Two polyoxometalate open framework (POMOF) materials have been synthesized using a secondary building unit (SBU) approach that facilitates the convergent assembly of multidimensional framework materials using a preassembled anionic SBU {P(8)W(48)}, with integrated "pore" 1 nm in diameter, and electrophilic manganese {Mn(2+)} linkers. This yields two new POMOFS with augmented hexagonal tiling (2 and 3), related to a known three-dimensional (3D) cubic array K(18)Li(6)[Mn(II)(8)(H(2)O)(48)P(8)W(48)O(184)]·108H(2)O (1), K(12)[Mn(II)(14)(H(2)O)(30)P(8)W(48)O(184)]·111H(2)O (2), and K(8)Li(4)[Mn(II)(14)(H(2)O)(26)P(8)W(48)O(184)]·105H(2)O (3). These frameworks have been crystallized from aqueous Li-buffered solutions of {P(8)W(48)} and Mn(II)(ClO(4))(2)·6H(2)O via careful control of the synthetic strategy akin to a crystal engineering approach using cation and temperature control to isolate different material architectures shown by compounds 1-3.     

Tetrakis(dimethyltin)-containing tungstophosphate [{Sn(CH3)2}4(H2P4W24O92)2]28-: first evidence for a lacunary Preyssler ion

We demonstrate for the first time that the superlacunary polyanion [H(2)P(4)W(24)O(94)](22)(-) reacts with electrophiles. One-pot reaction of this precursor polyanion with dimethyltin dichloride in aqueous acidic medium results in the hybrid organic-inorganic [{Sn(CH(3))(2)}(4)(H(2)P(4)W(24)O(92))(2)](28)(-) (1). Single-crystal X-ray analysis was carried out on K(17)Li(11)[{Sn(CH(3))(2)}(4)(H(2)P(4)W(24)O(92))(2)].51H(2)O (1a), which crystallizes in the tetragonal system, space group P4(2)/nmc, a = b = 21.5112(17) and c = 27.171(3) A, and Z = 2. Polyanion 1 is composed of two (P(4)W(24)O(92)) fragments that are linked by four equivalent diorganotin groups. The unprecedented assembly 1 has D(2)(d)() symmetry and contains a hydrophobic pocket in the center of the molecule. The cyclic voltammetry pattern of 1 is constituted by a first broad, 16-electron reduction wave followed by a second large current intensity wave. No splitting of the first reduction wave could be obtained at moderate scan rate values, even though two well-separated oxidation processes are associated with it. The characteristics of the first wave are clearly different from those obtained for the polyanion precursor [H(2)P(4)W(24)O(94)](22)(-) and the related, wheel-shaped [H(7)P(8)W(48)O(184)](33)(-), which is due to the {Sn(CH(3))(2)} fragments in 1. However, no feature was observed in the voltammogram which could be associated with reduction of the Sn centers.     

Crystal Structures of Ln（NO3）3（Ln=La,Yb）Complexes with 12—crown—4

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｓｏｆＬｎ（ＮＯ_３）_３（Ｌｎ＝Ｌａ，Ｙｂ）Ｃｏｍｐｌｅｘｅｓｗｉｔｈ１２－ｃｒｏｗｎ－４ＭａｏＪｉａｎｇ－Ｇａｏ；ＪｉｎＺｈｏｎｇ－Ｓｈｅｎｇ；ＹｕＦｅｎｇ－Ｌａｎ（ＬａｂｏｒａｔｏｒｙｏｆＲａｒｅＥａｒｔｈＣｈｅｍ...     

Effects of water uptake on the inherently oxygen-deficient compounds Ln26O27 square(BO3)8 (Ln=La, Nd)

The inherently oxygen-deficient compounds Ln26O27 square(BO3)8 (Ln=La, Nd) react with water vapor leading to Ln26O26(OH)2(BO3)8 phases, and this reaction is reversible. The crystal structure of Nd26O27 square(BO3)8 has been determined from single-crystal data (space group P with a=6.7643(10) A, b=12.663(2) A, c=14.271(2) A, alpha=90.553(8) degrees, beta=99.778(10) degrees, and gamma=90.511(9) degrees). It is a triclinic distorted version of the monoclinic structure of La26O27 square(BO3)8. The Ln26O26(OH)2(BO3)8 phases both crystallize in the monoclinic system (space group P21/c with a=6.7445(4) A, b=12.6177(9) A, c=14.4947(10) A, and beta=100.168(7) degrees for Nd26O26(OH)2(BO3)8 and a=6.9130(15) A, b=12.896(3) A, c=14.792(4) A, beta=99.698(16) degrees for La26O26(OH)2(BO3)8), and their crystal structure has been determined from single-crystal data, showing that the hydroxyl groups are localized mainly on one of the oxygen sites at room temperature (RT). For the Nd phases, the change in crystal system can result from two different phenomena depending on the atmosphere, either a phase transformation corresponding to a water uptake under wet conditions (triclinic Nd26O27 square(BO3)8 at RT-->monoclinic Nd26O26(OH)2(BO3)8) or a phase transition at approximately 300 degrees C for the anhydrous phase under dry conditions (triclinic Nd26O27 square(BO3)8 at RT-->monoclinic Nd26O27 square(BO3)8 at T>300 degrees C). For Nd26O26(OH)2(BO3)8, the conductivity measured under wet conditions at 300 degrees C is sigma300 degrees C approximately 0.5x10(-5) S cm(-1). Due to the dehydration process, the proton contribution to the total conductivity of the Nd phase is no longer observed above 500 degrees C whereas it was still clearly visible at 600 degrees C for the La phase.     

CRYSTAL STRUCTURES OF Ln(o-HOC_6H_4CO_2)_3 (H_2O)_2·2H_2O [Ln =Tb,Ho]

<正> Ln(o-HOC6H4CO2)3(H2O)2·2H2O [Ln = Tb, Ho], Mr = 642. 32 (648. 33 )**,monoclinic, space group Cc,a=16. 280(4)(16. 217 (2)) ,b= 14. 889(3) (14. 877(2)),c = 9.867(1)(9. 835(2)) A,β=101.49(1)(101. 46(1))°,Z= 4,V= 2343. 8(7)(2325. 3(6)) A3,Dc=1. 8(1. 85)g·cm-3,μ=31. 6(36. 1)cm-1(MoKa), F(000) = 1272(1280).The final R=0. 031(0. 031),Rw = 0. 029(0. 031). There is no discrete molecules of the compounds in the crystal structures. The compounds are in linear polymeric arrangements, each metal ion is bridged to the next by two bridging carboxyl groups from salicylato ions.     

A New Heteropolyoxotungstate with a Three-dimensional All-inorganic Framework [（C2H4N2）4（P4Co3W4O（28）H6）（H2C2O4）]n

A new heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006(17),b = 17.1006(7),c = 10.7525(5),V = 3144.2(2)3,Z = 4,Dc = 3.795 g·cm-3,F(000) = 3300,MoKα(λ = 0.71073 ),μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.     

Synthesis and reaction of the novel complex [AsPh4][OsCl5(H2O). X-ray structure analysis of [AsPh4][OsCl5(H2O)].2EtOH and [AsPh4][OsCl5(EtOH)].EtOH

The synthesis and characterization of the anionic mononuclear and homobinuclear osmium complexes [AsPh4][OsCl5L].xEtOH [L = H2O, x = 2 (9); L = EtOH, x = 1 (10a); L = py, x = 0 (10b)] and [AsPh4]2[Cl5Os(pyz)OsCl5] (12) (pyz = pyrazine) are described. Upon reduction in a chloride-containing medium, OsO4 (1) affords the osmium(IV) species [OsCl5(H2O)]- (2), which could be isolated by extraction with n-tributyl phosphate (TBP). Complex 9 is the first fully characterized chloroaquo complex of Os(IV). This complex is an effective starting material for the preparation of novel species, such as 10a, 10b, and 12. The X-ray structures of 9 and 10a were determined. Both compounds crystallize in the monoclinic space group P2(1)/n. 9: C28H34AsCl5O3Os, a = 10.910(4) A, b = 17.127(5) A, c = 17.555(7) A, beta = 103.77(2) degrees, V = 3186(2) A3, and Z = 4. 10a: C28H32AsCl5O2Os, a = 10.7762(2) A, b = 17.3939(1) A, c = 17.1477(3) A, beta = 103.645(1) degrees, V = 3123.45(8) A, and Z = 4. Complexes 9 and 10a crystallize with two and one molecule of EtOH and are bonded via hydrogen bridges to the H2O and EtOH ligand in 9 and 10a, respectively.