[CuL(H2O)2]{[CuL][Fe(CN)6]}2·2H2O (L=3,10-Bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane): A Novel Three-Dimensional Coordination Polymer via H-Bonded Linkages of One-Dimensional Zigzag Chain

A complex with the formula [CuL(H₂O)₂]{[CuL][Fe(CN)₆]}₂·2H₂O, where L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and crystallographically characterized. The structure is composed of a one-dimensional zigzag chain of units, and [CuL(H₂O)₂]²⁺ units. The one-dimensional zigzag chain extents through linkages. The adjacent two polymer chains are linked by the hydrogen bonding between [CuL(H₂O)₂]²⁺ and [Fe(CN)₆]^3–, forming a 3D supramolecular structure with inner hydrophilic channels. Magnetic susceptibility measurements show no exchange interaction between the Cu(II) and Fe(III) ions due to the longer (axial) bond length.     

Supramolecular Coordination Assemblies Using 2-Aminodiacetic Terephthalic Acid Ligands: K[NiII(Hadta)(H2O)2]·H2O and K[Cu 1.5 II (adta)(H2O)1.5]·H2O

Two new network structures, K[Ni^II(Hadta)(H₂O)₂]·H₂O (1) and K[Cu_1.5^II(adta)(H₂O)_1.5]·H₂O (2) which are stabilized by 2-aminodiacetic terephthalic acid ligands have been synthesized and structurally characterized. Supplemental analyses include infrared spectroscopy and CHN analysis. 1 contains mononuclear secondary building units that are linked through potassium counterions and H-bonds to form a 3D network structure. 2 contains a 1D coordination polymer containing Cu^II ions with two different coordination environments. Potassium counterions further network these 1D chain structures.     

Hydrothermal Synthesis, Crystal Structure and Characterization of New Coordination Polymer [Co2(pydc)2(H2O)6] n ·2nH2O

A coordination polymer of cobalt(II) containing the pyridine-2,5-dicarboxylate (pydc) ligand and having the composition [Co₂(pydc)₂(H₂O)₆] _n ·2nH₂O was prepared by the hydrothermal method. The coordination polymer was characterised by FTIR, single crystal XRD, SEM, TGA–DTA, and N₂ Temperature Programmed Desorption, Brunauer, Emmett and Teller surface area. The polymer contains two cobalt(II) ions with slightly distorted octahedral geometry. The carboxylate group at the 2-position of pyridine acts as a bridging ligand between two cobalt metal ions and this expansion leads to formation of a 1-D chain-like coordination polymer. The coordination polymer chains are packed together by well-directed hydrogen bonds to generate a three dimensional mesoporous network. The N₂ TPD study shows that the polymer is mesoporous in nature and possesses slit-shaped mesopores with average pore size diameter of 17.78 nm. SEM micrographs show well-defined channels in the solid crystals confirming the porosity of polymer. Thermogravimetric studies indicate the robust nature of the polymer. The polymer undergoes thermal decomposition in well-defined steps leading to the formation of cobaltous oxide as the end-product.     

Process for electroplating of highly pure and weldable gold coating using K{Au(Ⅰ)[CH2(CN)2]}2(C6H5O7)·H2O as main salt

以清洁环保的丙尔金[即一水合柠檬酸一钾二(丙二腈合金(Ⅰ))]代替有毒氰化亚金钾为主盐,用市售的可焊性镀金工艺配方及规范,生产高纯度(99.99％)的金镀层.所得镀金层呈浅柠檬黄色、无色斑,比亚硫酸盐纯金层更均匀、致密,金线键合强度经高低温循环试验后稳定,与载体焊接牢固、无空穴,满足美国军标MIL-STD-883H-2010中方法2011.8——键合强度测试规范的性能要求.镀金液性能与亚硫酸盐纯金镀液相近.镀金液使用3年多后,不论是在加热状态或是长期放置都很稳定.     

Oligocyanometallic cords as building blocks in luminescent three-dimensional coordination polymers: [Ag4Cd2(tren)2(CN)6.5][Ag(CN)1.5] and [Au2Cd(tren)(CN)4]·H2O

The syntheses, structures and luminescent properties of two unusual mixed-metal coordination polymers, namely [Ag₄Cd₂(tren)₂(CN)_7.5][Ag(CN)_1.5] 1 and [Au₂Cd(tren)(CN)₄]·H₂O 2 (tren = tris(2-aminoethyl)amine), are presented. Both compounds contain abnormal metal cords of oligocyanometallic anions as building blocks wherein the d¹⁰–d¹⁰ interaction plays a crucial role in the metal–metal assembly.     

Synthesis, Characterization and Crystal Structure of a Novel Three-Dimensional Supramolecular Framework Containing Ni···π Interaction Heteronuclear Complex: {[Cu(4(5)-Meim)4][Ni(CN)4] · H2O}n

The heteronuclear complex, {[Cu(4(5)-Meim)₄][Ni(CN)₄] · H₂O}_n (1), (4(5)-Meim = 4(5)-methylimidazole) was synthesized and characterized by FT-IR spectroscopy, single crystal X-ray diffraction, thermal analysis and elemental analysis. The Cu(II) ion has a distorted square planar geometry, extended to (4 + 2) weak coordination by two nitrogen atoms of the cyano group. The coordination sphere around the Ni(II) ion should be described as a 4 + 2 geometry with the four cyano groups and the axial coordination site is located at the imidazole ring though a weak Ni···π interaction. The coordination bond is much stronger than the Ni···π interactions and it is expected that the formation of the coordination bond will affect more significantly the position of the absorption bands associated with the vibrations of the ligand. In addition, the out-of-plane modes of 4(5)-Meim are shifted to higher frequencies relative to free ligand. We propose that these shifts are indicative of the weak CH∙∙∙π and Ni∙∙∙π interactions, according to the crystallographic and spectroscopic data.     

Synthesis, Structure and Electrochemical Property of a New Three-Dimensional Inorganic–Organic Vanadate Coordination Polymer [Cu2(bbi)2(V4O12)] · 4H2O (bbi = 1,1-(1,4-butanediyl)bis(imidazole))

A new inorganic–organic vanadate coordination polymer [Cu₂(bbi)₂(V₄O₁₂)] · 4H₂O (bbi = 1,1-(1,4-butanediyl)bis(imidazole)) (1) has been synthesized under hydrothermal condition and characterized by elemental analyses, IR spectra and single crystal X-ray diffraction. Structure analysis revealed that the three-dimensional structure of compound 1 is constructed from two-dimensional [Cu(bbi)₂]²⁺ layers linked through {V₄O₁₂}⁴⁻ building blocks. Compound 1 represents the first example of metal-organic frameworks with non-interpenetrated five-connected topological network (4⁶·6⁴) based on Cu(II) as nodes, bbi and {V₄O₁₂}⁴⁻ as mixed spacers. The electrochemical behavior of 1 modified carbon paste electrode (1-CPE) in 1M H₂SO₄ aqueous solution has been studied. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Metal–metal interaction through CH2–CN bridge: synthesis and characterization of [CpM(L2)NCCH2Fc]PF6 complexes (Fc=ferrocenyl; L=1/2 dppe,PPh3; M=Fe,Ru)

The new complexes [CpM(L₂)NCCH₂Fc]PF₆ (M=Fe 1, Ru 2; Fc=ferrocenyl), have been prepared from reaction of CpM(L₂)X and the ligand Fc–CH₂CN 3 in methanol and in the presence of NH₄PF₆. The compounds were characterized by elemental analysis as well as spectroscopic methods. Electrochemical as well as near-IR measurements suggest a weak metal–metal interaction for the Fe(II)–Fe(III) complex. Hush parameters for this mixed-valence complex suggest a class II Robin–Day type with a moderate metal–metal interaction similar to that observed in the related pyridine bridged systems (η⁵-C₅H₅)Fe-η⁵-C₅H₄–C₅H₄N–ML_n. The unusual electron transfer through a insulating CH₂ group is the first such example for an asymmetric binuclear system.     

A Novel Mixed-Valence Tetranuclear Iron-Oxygen Clusters in the Organically Templated Iron Phosphate [H3N(CH2)2NH3]2 Fe4O(PO4)4 ċH2O

A novel iron phosphate templated with ethylenediammonium cation, [H₃N(CH₂)₂NH₃]₂ Fe₄ O(PO₄)₄H₂O, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction, thermo-gravimetric analysis, magnetic susceptibility and Mossbauer spectroscopy. The compound crystallizes in the mono-clinic space group C2 with a= 30.3801(5),b= 10.1204(5),c= 10.0977(5) Å, = 107.712(1)°, V = 2957.5(4) ų and Z = 6. The structure contains 5 and 6-coordinated Fe atoms bridged by ₄-oxygen and PO₄ groups to form two types of mixed-valence Fe₄P₄ cubane-like clusters, which are connected via Fe- O- P bonds to give rise to intersecting channels that house the ethylenediammonium cations and water molecules. Room-temperature Mossbauer data confirm the presence of Fe^II and Fe^III.     

Synthesis,structural characterization and properties of a novel 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O

An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)₂][Cu(en)(H₂O)][(Cu(en)₂(H₂O)] [As^IIIAs^VMo₉O₃₄)]} · 2H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by elemental analyses, IR, UV and CD spectrum, powder X-ray diffraction, TG-DTA and single-crystal X-ray diffraction. The asymmetric unit of 1 consists of a monocapped trivacant Keggin [As^IIIAs^VMo₉O₃₄]^6 − subunit, a pendant [Cu(en)₂(H₂O)]^2 + cation, a pendant [Cu(en)(H₂O)]^2 + cation, one bridging [Cu(en)₂]^2 + cation and two lattice water molecules. It should be noted that 1 illustrates a one-dimensional (1D) helical chain assembled by {[Cu(en)(H₂O)][(Cu(en)₂(H₂O)][As^IIIAs^VMo₉O₃₄)]}^2 − clusters and [Cu(en)₂]^2 + linkers.     

A CeIII–CuII Supramolecular Architecture Based on a Trinuclear [Ce(H2O)6(CuL)2] Unit: Synthesis, Crystal Structure and Magnetic Properties

A novel 3d–4f heterometallic coordination complex [Ce(H₂O)₆ (CuL)₂]·NO₂·7H₂O (1) (H₃L = glycylglycine, N-[1-(2-hydroxy, phenyl)-propylidene]) was synthesized and characterized by IR, elemental analysis, TGA and single crystal X-ray diffraction. An octameric water cluster consisting of a planar tetrameric water ring and four dangling water molecules were observed in 1. Variable-temperature magnetic data shows antiferromagnetic behavior for 1.     

A new mixed-ligand one dimensional complex via hydrogen bonds: Cu(Mal)(bpy)·2H2O (Mal=Malonate ion,bpy=2,2′-bipyridine)

A new hydrogen-bonded one dimensional complex, Cu(Mal)(bpy)·2H₂O (Mal=Malonate ion, bpy=2,2′-bipyridine), has been synthesized and characterized by X-ray single crystal structure analysis. The copper atom is five-coordinated in a distorted square pyramidal environment to two oxygen atoms of Mal, two nitrogen atoms of the bpy ligand and an oxygen atom of water. The IR, electronic spectrum and ESR of the title compound have been studied.     

Oxidation of cobalt(II) to cobalt(III) in the presence of phosphorus and sulphur donors via –O–C bond cleavage: synthesis and structure of [CoIII(dppe)(EtOCS2)(COS2)] (dppe=1,2-bis(diphenyl phosphino)ethane)

An ethanolic solution of cobalt(II) reacts with dppe (1,2-bis(diphenyl phosphino)ethane) and etxant (ethyl xanthate) affording an intensely coloured Co^III complex, [Co^III(dppe)(etxant)(COS₂)], by eliminating [EtOC(S)(SEt)] via –O–C bond rupture. The structure of the cobalt(III) complex has been confirmed by X-ray crystallography, NMR and mass spectrometry.     

Metal‐Free [4+2] Annulation of Arylalkynes with tert‐Butyl Nitrite through C(sp2)?H Oxidation to Assemble Benzo[e][1,2]oxazin‐4‐ones

A metal‐free radical‐mediated [4+2] annulation of internal arylalkynes with tert‐butyl nitrite (t‐BuONO) is presented for the synthesis of benzo[e][1,2]oxazin‐4‐ones through the addition of t‐BuONO across the CC triple bond, hydration, isomerization and aromatic C(sp²) H oxidation cascades. The ¹⁸O‐labeling experiment shows that two oxygen atoms in the product system are from water.

     

Synthesis, Supramolecular Architecture and DNA Binding Studies of a Novel Heterotrinuclear FeIII/CoII/FeIII Complex: [Co(phen)2][Fe(phen)(CN)4]2·4H2O (phen?=?1,10-phenanthroline)

A novel cyano-bridged heterotrinuclear Fe^III/Co^II/Fe^III complex, [Co(phen)₂][Fe(phen)(CN)₄]₂·4H₂O (1) (phen = 1,10-phenanthroline), has been synthesized under solvothermal conditions, and characterized by elemental analysis, FI-IR spectrum and single-crystal X-ray diffraction. The structure analysis reveals complex 1 is constructed into a 3D supramolecular architecture through abundant intermolecular non-covalent interactions. According to the supramolecular self-assembly of complex 1, five types of π–π stacking models of phenanthroline ligands, hydrogen bonds formed by four lattice water molecules, and C–H···N weak interactions involving cyano groups are all observed. Electronic absorption spectroscopy and fluorescence titration studies of the interaction between complex 1 and calf thymus DNA are suggestive of an intercalative binding mode with an intrinsic binding constant of 7.95 × 10³ M⁻¹ and a linear Stern–Volmer quenching constant of 1.033 × 10⁵ M⁻¹.     

Preparation of a Novel Nano-scale Lead (II) Zig-Zag Metal–Organic Coordination Polymer with Ultrasonic Assistance: Synthesis,Crystal Structure,Thermal Properties,and NBO Analysis of [Pb(μ-2-pinh)N<Subscript>3</Subscript> H<Subscript>2</Subscript>O]<Subscript>n</Subscript>

A novel nano-cauliflower-shaped lead(II) metal–organic coordination polymer, [Pb(μ-2-pinh)N₃ H₂O]_n (1), was synthesized using an ultrasonic method. The nanostructure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction, IR spectroscopy, elemental analysis, and thermal analysis. The compound was structurally characterized by single-crystal X-ray diffraction. The coordination compound takes the form of a zig-zag one-dimensional polymer in solid state. The coordination number of the lead(II) ions is six (PbN₄O₂) with three nitrogen atoms and one oxygen atom from two linker organic ligands, as well as one oxygen from coordinated water and one nitrogen atom from terminal coordinated azide anion. It has a stereo-chemically active lone electron pair, and the coordination sphere is hemidirected. The zig-zag 1D chains interact with neighbouring chains through weak interactions, creating a 3D supramolecular metal–organic framework. Lead oxide nanoparticles were obtained by thermolysis of the new nano coordination compound at 180 °C with oleic acid as a surfactant. The morphology and size were further studied using SEM. Natural bond orbital analyses demonstrate the electronic properties of the lead centre and other atoms.