New α,ω-dicarboxylate coordination polymers with 4,4′-bipyridine: Cu(bpy)(C5H6O4), Zn(bpy)(C5H6O4), Zn(bpy)(C6H8O4) and Mn(bpy)(C8H12O4) · H2O

Four 4,4′-bipyridine α,ω-dicarboxylate coordination polymers Cu(bpy)(C₅H₆O₄) (1), Zn(bpy)(C₅H₆O₄) (2), Zn(bpy)(C₆H₈O₄) (3) and Mn(bpy)(C₈H₁₂O₄) · H₂O (4) have been synthesized and structurally characterized by single crystal X-ray diffraction methods (bpy = 4,4-bipyridine, (C₅H₆O₄)²⁻ = glutarate anion, (C₆H₈O₄)²⁻ = adipate anion, (C₈H₁₂O₄)²⁻ = suberate anion). Their crystal structures are featured by dimeric metal units, which are co-bridged by 4,4′-bipyridine ligands and dicarboxylate anions such as glutarate, adipate and suberate anions to generate 2D layers with a (4,4) topology in 1, 2 and 4 as well as to form 3D frameworks in 3. Two 3D frameworks in 3 interpenetrate with each other to form a topology identical to the well-known Nb₆F₁₅ cluster compound. Over 5–300 K, the paramagnetic behavior of 4 follows the Curie–Weiss law χ_m(T − Θ) = 4.265(5) cm³ mol⁻¹ with the Weiss constant Θ = −6.3(2) K. Furthermore, the thermal behavior of 3 and 4 is also discussed.     

Coordination polymers of macrocyclic oxamide with 1,3,5-benzenetricarboxylate: syntheses, crystal structures and magnetic properties

Solvothermal reactions of mixed ligands H(3)BTC and macrocyclic oxamide complexes (ML, M = Cu, Ni) with M(ClO(4))(2)·6H(2)O (M = Co, Zn, Ni and Cd) afford six new complexes, including [M'(4)(BTC)(2)(ML)(2)(OH)(2)(H(2)O)(2)]·2H(2)O (M' = Co, M = Ni, for (1); M' = Zn, M = Ni, for (2); M' = Zn, M = Cu, for (3)), [Ni(3)(BTC)(2)(NiL)(2)(H(2)O)(6)]·2CH(3)OH·2H(2)O (4), [Cd(4)(BTC)(2)(HBTC)(NiL)(4)(H(2)O)]·3H(2)O (5) and [Cd(HBTC)(CuL)]·H(2)O (6) (ML, H(2)L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; H(3)BTC = 1,3,5-benzenetricarboxylic acid). Complexes 1-3 consist of a 2D layer framework formed by the linkage of M(II)(M = Ni, Cu) and M'(4) (M' = Co, Zn) cluster via the oxamide and BTC(3-) bridges and display a (3,6)-connected network with a (4(3))(2)(4(6).6(6).8(3)) topology. The structure of 4 consists of pentanuclear [Ni(II)(5)] units and arranges in a 1D cluster chain. Complex 5 exhibits a 2D layered structure characterized by 3,4,3-connected (4.6(2))(3)(4.6(3).8(2))(4(2).6(3).8)(4(2).6) topology. Complex 6 possesses a 3D network with sra topology. The magnetic properties of complexes 1 and 4 were investigated.     

Synthesis and X-ray crystal structures of Cs2[W(bpy)(CN)6]·2H2O and (AsPh4)2[W(bpy)(CN)6]·3.5H2O

The synthesis, spectral properties and crystal structures of Cs₂[W(bpy)(CN)₆]·2H₂O and (AsPh₄)₂[W(bpy)(CN)₆]·3.5H₂O are described. The anions of both salts show distorted antiprismatic geometry with very similar bond lengths and angles. The structure of the [W(bpy)(CN)₆]^2– anion is independent of the type of cation, in contrast to the octacyanotungstate(IV).     

Topological evolution in uranyl dicarboxylates: synthesis and structures of one-dimensional UO2(C6H8O4)(H2O)2 and three-dimensional UO2(C6H8O4)

Two novel uranyl adipates are reported as synthesized via hydrothermal treatment of uranium oxynitrate and adipic acid. One-dimensional UO(2)(C(6)H(8)O(4))(H(2)O)(2) (1) [a = 9.6306(6) A, c = 11.8125(10) A, tetragonal, P4(3)2(1)2 (No. 96), Z = 4] consists of chains of (UO(2))O(4)(H(2)O)(2) hexagonal bipyramids tethered through a linear adipic acid backbone. Three-dimensional UO(2)(C(6)H(8)O(4)) (2) [a = 5.5835(12) A, b = 8.791(2) A, c = 9.2976(17) A, alpha = 87.769(9) degrees, beta = 78.957(8) degrees, gamma = 81.365(11) degrees, triclinic, P1 (No. 2), Z = 2] is produced by decreasing the hydration level of the reaction conditions. This structure contains a previously unreported [(UO(2))(2)O(8)] building unit cross-linked into a neutral metal-organic framework topology with vacant channels.     

The hydrothermal syntheses and characterization of one- and two-dimensional structures constructed from metal-organic derivatives of polyoxometalates: [(Cu(bpy)2)(Cu(bpy)(H2O))(Mo5O15)(O3P(CH2)4PO3)].H2O and [(u2(tpypyz)(H2O)2)(Mo5O15)(O3PCH2CH2PO3)].5.5H2O [bpy = 2,2'-bipyridine,tpypyz = tetra(2-pyridyl)pyrazine

The hydrothermal reaction of CuSO(4).5H2O, Na2MoO(4).2H2O and 2,2'-bipyridine with the bridging diphosphonate ligand H2O3P(CH2)4PO3H2 yields the one-dimensional chain [(Cu(bpy)2)(Cu(bpy)(H2O)2)(Mo5O15)(O3P(CH2)4PO3)].H2O; the introduction of a second bridging component in the reaction of Cu(MeCO2)2.H2O, MoO3, H2O3PCH2CH2PO3H2 and tetra(2-pyridyl)pyrazine yields the network solid [(Cu2(tpypyz)(H2O)2)(Mo5O15)(O3PCH2CH2PO3)].5.5H2O.     

Coordination complexes of 2-(4-quinolyl)nitronyl nitroxide with M(hfac)(2) [M = Mn(II), Co(II), and Cu(II)]: syntheses, crystal structures, and magnetic characterization

Three new complexes of the formula M(2)L(2) derived from 2-(4-quinolyl)nitronyl nitroxide (4-QNNN) and M(hfac)(2) [M = Mn(II), Co(II), and Cu(II)], (4-QNNN)(2).[Mn(hfac)(2)](2) (1), (4-QNNN)(2).[Co(hfac)(2)](2).2H(2)O (2), and (4-QNNN)(2).Cu(hfac)(2).Cu'(hfac)(2) (3), were synthesized and characterized structurally as well as magnetically. Complexes 1 and 2 are four-spin complexes with quadrangle geometry, in which both the nitrogen atoms of quinoline rings and oxygen atoms of nitronyl nitroxides are involved in the formation of coordination bonds. For complex 3, however, the nitrogen atoms of quinoline rings are coordinated with Cu(II) ion to afford a three-spin complex, which is further linked to another molecule of Cu(hfac)(2) (referred to as Cu'(hfac)(2)) to form a 1D alternating chain. The magnetic behaviors of the three complexes were investigated. For complex 1, as the nitronyl nitroxides and Mn(II) ions are strongly antiferromagnetically coupled, consequently its temperature dependence of magnetic susceptibility was fitted to the model of spin-dimer with S = 2, yielding the intradimer magnetic exchange constant of J = -0.82 cm(-1). For complex 2, the temperature dependence of the magnetic susceptibility in the T > 50 K region was simulated with the model of two-spin unit with S(1) = 3/2 and S(2) = 1/2, leading to J = -321.9 cm(-1) for the magnetic interaction due to Co(II).O coordination bonding, D = -16.3 cm(-1) (the zero-field splitting parameter), g = 2.26, and zJ = -3.8 cm(-1) for the magnetic interactions between Co(II) ions and nitronyl nitroxides through quinoline rings and those between nitronyl nitroxides due to the short O.O short contacts. The temperature dependence of magnetic susceptibility of 3 was approximately fitted to a model described previously affording J(1) = -6.52 cm(-1) and J(2) = 3.64 cm(-1) for the magnetic interaction between nitronyl nitroxides and Cu(II) ions through the quinoline unit via spin polarization mechanism and the weak O.Cu coordination bonding, respectively.     

Comparison of two polymeric transition metal complexes with 1,4‐benzenedicarboxylate ions as bridging ligands, [Co(C8H4O4)(C12H8N2)(H2O)] and [Cu(C8H4O4)(C10H9N3)]·H2O

The title complexes, catena‐poly[[aqua(1,10‐phenanthroline‐κ²N,N′)­cobalt(II)]‐μ‐benzene‐1,4‐di­carboxyl­ato‐κ²O¹:O⁴], [Co(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)], (I), and catena‐poly[[[(di‐2‐pyridyl‐κN‐amine)copper(II)]‐μ‐benzene‐1,4‐di­carboxyl­ato‐κ⁴O¹,O^1′:O⁴,O^4′] hydrate], [Cu(C₈H₄O₄)(C₁₀H₉N₃)]·H₂O, (II), take the form of zigzag chains, with the 1,4‐benzene­di­carboxyl­ate ion acting as an amphimonodentate ligand in (I) and a bis‐bidentate ligand in (II). The Co^II ion in (I) is five‐coordinate and has a distorted trigonal–bipyramidal geometry. The Cu^II ion in (II) is in a very distorted octahedral 4+2 environment, with the octahedron elongated along the trans O—Cu—O bonds and with a trans O—Cu—O angle of only 137.22 (8)°.     

Coordination polymers with adamantanediacetate bridges: syntheses, structures, and magnetic properties

Abstract  Two new coordination polymers, [CoL(bpp)] _n (1) and [MnL(bipy)] _n ·0.25nH₂L·0.5nH₂O (2) (H₂L = 1,3-adamantanediacetic acid, bpp = 1,3-bis(4-pyridyl)propane, bipy = 4,4′-bipyridine), were synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, and thermal analysis. Complex 1 is an one-dimensional (1D) chain structure of Co(II) bridged by L²⁻ as well as bpp. Complex 2 consists of a two-dimensional (2D) (3,6)-connected topology layer structure. Variable temperature magnetic susceptibility measurements in the range of 2–300 K reveal the existence of weak antiferromagnetic interactions in two complexes with J = −1.74 cm⁻¹, g = 2.26 for 1 and J = −0.10 cm⁻¹, g = 1.67 for 2. Index abstract  Two mental-organic frameworks, namely [CoL(bpp)] _n (1) and [MnL(bipy)] _n ·0.25nH₂L·0.5nH₂O (2) (H₂L = 1,3-adamantanediacetic acid, bpp = 1,3-bis(4-pyridyl)propane, bipy = 4,4′-bipyridine), have been synthesized based on 1,3-adamantanediacetic acid and N-donor coligand with metal ions Co(II) and Mn(II). The magnetic measurement of the two polymers reveals typical antiferromagnetism exchange. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Copper(II) coordination polymers constructed from aromatic polycarboxylate and flexible triazole ligands with different spacer lengths: syntheses,structures, and properties

{[Cu₂(btm)₂(Hbtc)(H₂btc)₂(H₂O)]·9.5H₂O}_n (1), [Cu(bte)(H₂btc)₂]_n (2) {[Cu(btp)(H₂btc)₂]·0.25H₂O}_n (3) (btm?=?bis(1,2,4-triazol-1-yl)methane, bte?=?bis(1,2,4-triazol-1-yl)ethane, btp?=?bis(1,2,4-triazol-1-yl)propane, H₃btc?=?benzene-1, 3, 5-tricarboxylic acid) have been synthesized and structurally characterized. 1 features a 1-D double chain, which is interconnected by classical hydrogen-bonding (O–H?O) and π–π interactions to lead to a 3-D supramolecular architecture. 2 and 3 are both 1-D single chains, which are interconnected by π–π interactions to 2-D layer architectures. Elemental analysis, XRD, IR, TG and EPR spectra have been carried out and discussed.     

Ionization efficiencies of C3H6, C4H8, C6H12, C2H6O,and C3H8O isomers

Ionization efficiencies of 14 organic compounds have been measured in the wavelength region from 105 to 134nm using an ionization chamber. The compounds examined are cyclopropane, propylene, l-butene, isobutene, cis-and trans-2-butenes, cyclohexane, 1-hexane, tetramethylethylene, ethyl alcohol, dimethyl ether, n-, and iso-propyl alcohol, and ethyl methyl ether. The ionization efficiencies of cyclopropane and cyclohexane monotonically increase with increasing photon energy, but those for the others show a peak or a shoulder in the wavelength region of the present work.