Inorganic Chemistry Communications (v.12, #5)

Contents List (iii-x).

A fast and easy approach to the synthesis of Zeise’s salt using microwave heating by Krista A. Shoemaker; Nicholas E. Leadbeater (341-342).
A fast and easy approach to the synthesis of Zeise’s salt, KPtCl3(C2H4), is reported using microwave heating. The reaction is complete after 15 min at 130 °C using K2PtCl4 as starting material, a 1:1:1 ratio of water:ethanol:concentrated HCl as solvent, and a loading of 50 psi of ethene.A fast and easy approach to the synthesis of Zeise’s salt, KPtCl3(C2H4), is reported using microwave heating. The reaction is complete after 15 min at 130 °C using K2PtCl4 as starting material, a 1:1:1 ratio of water:ethanol:concentrated HCl as solvent, and a loading of 50 psi of ethene.
Keywords: Microwave; Platinum; Zeise’s salt; Alkene complex;

HPLC separation, NMR and QTOF/MS/MS structure elucidation of a prominent nitric oxide donor agent based on an isomeric composition of a nitrosyl ruthenium complex by Anderson Rodrigo Moraes de Oliveira; Franciane Marquele-Oliveira; Danielle Cristine Almeida Silva de Santana; Sofia Nikolaou; Pierina Sueli Bonato; Roberto Santana da Silva (343-346).
The two possible isomers for the nitric oxide donor [Ru(terpy)(bdqi-COOH)NO](PF6)3 complex have been isolated by HPLC and characterized by ESI MS/MS and NMR measurements.A new and promising nitrosyl ruthenium complex, [Ru(NO)(bdqi-COOH)(terpy)](PF6)3, bdqi-COOH is 3,4-diiminebenzoic acid and terpy is 2,2′-terpyridine, has been synthesized as a NO donor agent. The procedure used for [Ru(NO)(bdqi-COOH)(terpy)](PF6)3 synthesis has, apparently, yielded the formation of two isomers in which the ligand bdqi-COOH appears to be coordinated in its reduced form (bdcat-COOH), which could have differences in their pharmacological properties. Therefore, it was intended to separate the two possible isomers by high-performance liquid chromatography (HPLC) and to characterize them by high resolution mass spectrometry (QTOF MS) and by magnetic nuclear resonance spectroscopy (NMR). The results obtained by MS showed that the ESI-MS mass spectra of both HPLC column fractions, e.g. peak 1 and peak 2, are essentially equal, showing that both isomers display nearly identical gas-phase behavior with clusters of isotopologue ions centered at m/z 573, m/z 543 and m/z 513. Regarding the NMR analysis, the results showed that the positional isomerism is located in the bdqi-COOH ligand. From the observed results it can be concluded that the synthesis procedure that has been used results in the formation of two [Ru(terpy)(bdqi-COOH)NO](PF6)3 isomers.
Keywords: Nitrosyl ruthenium complex; Nitric oxide donors; Isomerization of ruthenium complex; Structure elucidation of ruthenium complex;

Dissociation of C60 from Ir(CO)(PPh3)2(Cl)(η 2-C60) in a binary mixture of solvents (solvent1 and solvent2) produced non-equilibrium mixtures of Ir(CO)(PPh3)2(Cl)(solvent1) and Ir(CO)(PPh3)2(Cl)(solvent2). Once the solvated species were produced, they underwent a relative fast solvent exchange between them to produce an equilibrium mixture.Dissociation of C60 from Ir(CO)(PPh3)2(Cl)(η 2-C60) in a binary mixture of solvents (solvent1 and solvent2) produced non-equilibrium mixtures of Ir(CO)(PPh3)2(Cl)(solvent1) and Ir(CO)(PPh3)2(Cl)(solvent2). Once the solvated species were produced, they underwent a relative fast solvent exchange between them to produce an equilibrium mixture.
Keywords: Vaska’s complex; Oxidative addition; Solvent exchange;

Synthesis and characterization of strontium 1,3,5-benzenetricarboxylate, [Sr3(1,3,5-BTC)2(H2O)4]·H2O by Dat T. Tran; Deryn. Chu; Allen G. Oliver; Scott R.J. Oliver (351-354).
A 3-D metal-organic framework, strontium 1,3,5-benzenetricarboxylate, [Sr3(1,3,5-BTC)2(H2O)4]·H2O, is described. The coordination framework contains three distinct Sr centers, one of which is seven-coordinate and the other two are nine-coordinate geometry. The phenyl rings form a herring-bone type of arrangement down the a-axis.A three-dimensional strontium-based metal-organic framework was constructed using 1,3,5-benzenetricarboxylic acid, [Sr3((OOC)3C6H3)2(H2O)4]·H2O. This new compound was synthesized hydrothermally and is a rare example of a strontium metal-organic network. The compound network contains three distinct Sr centers, one of which is seven-coordinate and the other two are nine-coordinate geometry. The benzene rings form a herring-bone type of arrangement down the a-axis. The material is thermally stable to ca. 230 °C and transforms to an unknown material before finally decomposing to phase-pure SrCO3 at 650 °C. The synthesis, structure, morphology and materials properties are discussed.
Keywords: Hydrothermal synthesis; 1,3,5-benzenetricarboxylic acid; Strontium 1,3,5-benzenetricarboxylate; Metal-organic framework;

Compound [Bu4N]2[Ni(ppdt)2] (1) exhibits reversible acid–base behavior upon the addition of 10 μL aliquots of a dilute CH3COOH solution in forward reaction and 10 μL aliquots of a dilute NH3 solution in the backward reaction through protonation and deprotonation of the imine nitrogens of dithiolate ligands in MeOH solutions. Compound 1 shows an interesting supramolecular network in its solid state.The compound [Bu4N]2[Ni(ppdt)2] (1) (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) has been synthesized, starting from pyrido[2,3-b]pyrazine-2,3-dithiol, nickel chloride and tetrabutylammonium bromide in methanol. Compound 1 crystallizes in P21/c space group (monoclinic system). Its crystal structure is characterized by interesting C–H⋯S and C–H⋯N supramolecular weak interactions. Its solution state has been described with acid–base (protonation–deprotonation) behavior, that has rarely been investigated for a metal–dithiolene system. Compound 1 is first instance of a metal–dithiolene compound that has three ring nitrogen on each dithiolate ligand. The pH dependent changes in the charge-transfer absorption band are attributed to the protonation on an imine nitrogen of the ppdt ligand. The complex is electrochemically quasi-reversible with an oxidation potential of E 1/2  = +0.46 V vs. Ag/AgCl in methanol.
Keywords: Nickel(II)-dithiolene; Crystal structure; Supramolecular chemistry; Acid–base behavior;

In this work, Fe(II) complexes with hexaaza macrocyclic ligand were entrapped in nanoreactor of zeolite-Y. The new Fe(II) complex nanoparticles have been characterized by various techniques such as: FT-IR, BET, XPS, TGA techniques and so on.Iron(II) complexes with 18- and 20-membered hexaaza macrocyclic ligands were entrapped in the nanoreactors of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)iron(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Fe(N–N)2]2+–NaY; in the nanoreactors of the zeolite, and (ii) template condensation of the iron(II) precursor complex with 2,6-diacetylpyridine.The mode of bonding and overall geometry of the complexes and new complex nanoparticles entrapped in the nanoreactor of zeolite-Y ([Fe([18 or 20]py2N4)]2+–NaY, [Fe(Bzo2[18 or 20]py2N4)]2+–NaY) has been inferred through FT-IR, TGA, XRD, XPS spectroscopic techniques and elemental analysis as well as nitrogen adsorption.
Keywords: Complex nanoparticles; Hexaaza; Iron(II); Zeolite encapsulation;

Compound [NiII(C6H4(NH2)2)2(NO2)2] (1) exhibits the thermochromism in solid state driven by reversible linkage isomerization of –NO2 to –ONO. This is accompanied by color change from red to blue as is evidenced from the pictures of crystals at different stages.A simple mono-nuclear nickel(II) complex [NiII{C6H4(NH2)2}2(NO2)2] (1) has been synthesized from an aqueous solution containing nickel chloride, sodium nitrite and ortho-phenylenediamine (opda). When crystals of compound 1 are heated in the temperature range of 110–120 °C for 5 min, their brown color changes to blue, that is accompanied by the conversion of nitro group (N-coordinated) in compound 1 into nitrito group (O-coordinated) in compound [NiII{C6H4(NH2)2}2(ONO)2] (2). On cooling, the nitrito compound 2 goes back to parent nitro-compound 1.
Keywords: Nickel mono-nuclear complex; Crystal structure; Nitro–nitrito conversion; Thermochromic properties; Reversible solid state reaction;

The crystallisation of [Pd(bedp)]Cl2 (bedp = 1,4-bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl] piperazine) in DMSO yields the unexpected compound [Pd(bedp)][Pd2Cl4-SMe)2]. The most surprising feature is the formation of the anion [ Pd 2 Cl 4 ( μ -SMe k ) 2 ] 2 - , as this anion had not been previously described in the literature.Crystallisation of [Pd(bedp)]Cl2 (bedp = 1,4-bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl] piperazine) in DMSO affords the compound [Pd(bedp)][Pd2Cl4(μ-SMe)2], where the cation complex is mononuclear and the anion complex is dinuclear. The most surprising feature is the formation of the anion [ Pd 2 Cl 4 ( μ -SMe ) 2 ] 2 - , as this anion has not been described in the literature. In this anion, each palladium atom is coordinated by two thiolate bridging sulfurs and two terminal chlorides.
Keywords: Palladium complex; Binuclear complex; Pyrazole ligand; μ-Methylthiolate;

A novel Zn(II) framework with 3-fold interpenetrating α-polonium topology by Guo-Hua Wei; Jin Yang; Ying-Ying Liu; Jian-Fang Ma; Ji-Cheng Ma (371-374).
The title compound displays a rare 3-fold interpenetrated α-polonium-type network which is built from bimetallic cores as six-connected nodes.A novel coordination polymer [Zn2(dbi)(m-BDC)2] n (1), where dbi = 1,1′-(1,10-decanediyl)bis(imidazole) and m-BDC = 1,3-benzenedicarboxylate anion, has been isolated under hydrothermal condition and characterized by single-crystal X-ray diffraction. The compound 1 displays a 3-fold interpenetrated α-polonium-type network, which is built from bimetallic cores as six-connected nodes. Thermal gravimetric analysis (TGA) and luminescent property for 1 are discussed in detail.
Keywords: Coordination polymer; 1,1′-(1,10-Decanediyl)bis(imidazole); Interpenetrated; α-Polonium;

A luminescent [Ag3S3] n -tube based metal–organic framework by Zheng-Ming Hao; Hu-Ping Liu; Huan-Huan Han; Wan-Ting Wang; Xian-Ming Zhang (375-377).
Solvothermal treatment of silver nitrate, pyridine-4-thione (4-pdtH) and NH4SCN at 140 °C for 3 days produced a three-dimensional metal–organic framework [Ag3(4-pdt)(SCN)2] (1) in which [Ag3S3] n tubes act as building units and pyridine rings and CN groups act as linkers.Solvothermal treatment of silver nitrate, pyridine-4-thione (4-pdtH) and NH4SCN at 140 °C for 3 days produced a three-dimensional metal–organic framework [Ag3(4-pdt)(SCN)2] (1) in which [Ag3S3] n tubes act as secondary building units and pyridine rings and CN groups act as linkers. At ambient temperature, 1 shows a blue emission band assigned as from a ligand-centred n → π or π → π process.
Keywords: AgS tube; Pyridine-4-thione; Coordination polymer; Luminescence;

Electrochemiluminescence studies of phosphine chelated osmium(II) complexes by Gonzalo Angulo; Andrzej Kapturkiewicz; Sheng-Yuan Chang; Yun Chi (378-381).
Intense yellow/orange electrochemiluminescence (ECL) emission osmium(II) complexes − Os(L2L′) − have been generated by means of the electron transfer reaction between Os(L2L′)+ and Os(L2L′) as well as Os(L2L’)+ and 1-cyanonaphtalene= species in acetonitrile/dioxan (1:1) solutions. High ECL efficiencies, up to five times higher than that of the famous Ru ( bipy ) 3 2 + based ECL systems, have been found.The electrochemiluminescence (ECL) properties of five different yellow/orange emissive osmium(II) complexes of general formula Os(L2L’) with three different kinds of bidentate phosphine ligands L’ have been studied in acetonitrile/dioxane 1:1 solution by means of the triple-potential-step technique. The investigated complexes contain either two substituted pyrazolate or triazolate ligands L. The obtained ECL results have been interpreted in terms of the ligands nature, showing that the efficiency of ECL seems to be sensitive to the π-acidity of the phosphine ligand. To the authors’ best knowledge, the reported ECL efficiencies are the highest found for Os(II) complexes under similar conditions to date, that are at maximum five times higher than that of the famous Ru ( bipy ) 3 2 + based ECL systems.
Keywords: Osmium(II) complexes; Chelating phosphine ligands; N-donors; Electrochemiluminescence;

A new C 2-symmetric diaza-crown ether–CuII mononuclear complex containing 1,2,3-triazole ligands by Jean-Pierre Joly; Marc Beley; Katalin Selmeczi; Emmanuel Wenger (382-384).
A new C 2-symmetric lariat ether containing two [1,2,3]triazolo-ligands as sidearms was synthesized via a click chemistry approach. The ligand (2) readily forms a stable 1:1-complex with Cu(ClO4)2. The resulting complex (3) was characterized by X-ray crystallography, IR, elemental analysis, MS, UV–Vis and EPR. The cyclic voltammetry of the complex was performed in DMF.A novel C 2-symmetric lariat ether containing two [1,2,3]triazolo-ligands as sidearms was prepared via a click chemistry approach from known N,N′-dipropargyl-4,13-diaza-18-crown-6 (1). The ligand (2) readily forms a stable 1:1-complex with cupric perchlorate. A single crystal structure of the centro-symmetric mononuclear complex (3) could be determined. The CuII center displays a distorted six-coordinated octahedral geometry where two triazoles and two pivot nitrogens constitute the basal plane. The axial positions are occupied by two oxygens of the crown ether part. The cyclic voltammograms of a DMF solution of the complex showed two redox processes in our experimental conditions.
Keywords: Diaza-crown ether; [1,2,3]Triazole; CuII complex; X-ray structure; Cyclic voltammetry;

The structure of Ln–Ag coordination compounds [LnAg2(IN)4(OAC) · 5H2O] · 2H2O (Ln = Gd 1, Eu 2) shows the 1-D chain-like structure constructed by the linkages of Ag–Ag between neighboring links conformed by isonicotinic acids bridging silver centers and Ln–carboxylate chains, the dissociative acetic groups and water molecules spread around the chains. The two compounds exhibited different luminescent properties upon excitation.Two novel Ln–Ag coordination compounds with the formula [LnAg2(IN)4(OAC) · 5H2O] · 2H2O (Ln = Gd 1, Eu 2; HIN = isonicotinic acid; HOAC = acetic acid) have been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction, thermal analysis, IR absorption spectroscopy, ultraviolet excitation and emission spectrum. The two compounds show isostructural architectures and exhibit an unusual 1-D structure, which is formed by the linkages of Ag–Ag.
Keywords: Ln–Ag; 1-D structure; Hydrothermal synthesis; Luminescence;

A novel erbium(III) coordination polymer represents the three-dimensional framework constructed via bridging oxalate and pydc mixed ligands, in which supramolecular left-handed and right-handed helices were further connected via μ4-oxolate anion, the final three-dimensional racemic framework can be considered as being constructed by helix-linked scalelike network, with one-dimensional channels filled with the coordinated water molecules as well as lattice–water molecules, and the structure is a binodal (three, four)-connected nodes net, with the Schläfli symbol (63  · 83)(83)(6 · 83).Reaction of 2,6-pyridine-dicarboxylic acid and ammonium oxalate with erbium salt results in the formation of a self-assembly network based upon mixed ligands of oxalate and pyridine-dicarboxylate formulated as {[Er4(pydc)24-C2O4)4]·8H2O·6H2O} n (H2pydc = 2,6-pyridine-dicarboxylic acid), in which supramolecular left-handed and right-handed helices are connected via μ4-oxalate anions, and gave the 1D coordination channels constructed via bridging oxalate and pydc ligands. The complex also displayed photo-luminescent properties in the solid state at room temperature.
Keywords: Lanthanide-organic frameworks; Oxalate bridged; Chirality; Luminescence;

Synthesis, structure and electrochemical properties of the cationic complex tris-(imidazolidine-1,10-phenanthroline)iron(II) by Camilo García; Diego Villagra; Francesco Caruso; Miriam Rossi; Betty Matsuhiro; Leonora Mendoza; María J. Aguirre; Mauricio Isaacs (392-395).
The complex [FeII(Imz-phen)3](PF6)2, (Imz-phen = imidazolidine-[4,5-f]-1,10-phenanthroline), has been prepared and characterized using X-ray diffraction and spectroscopic techniques. A film is generated by cyclic voltammetry. The film shows electrocatalytic properties in the reduction of S(IV) oxoanions in ethanol/water solution.The complex [FeII(Imz-phen)3](PF6)2, (Imz-phen = imidazolidine-[4,5-f]-1,10-phenanthroline) has been prepared and characterized using X-ray diffraction, UV–vis and IR spectroscopy, elemental analysis, fast atomic bombardment (FAB) mass spectrometry, and cyclic voltammetry. Its crystal lattice includes acetonitrile (π–π bound to phenanthroline), methanol, and water molecules. Scanning continuously between 1000 mV and 1650 mV in CH3CN, a modified electrode that includes the iron (II) complex is obtained; after the 25th continuous cycle a stable film is formed that is electrocatalytically active in the reduction of sulfur oxoanions. When the electrocatalytic properties are evaluated in ethanol/water solution, the current achieved from the electroreduction of these sulfur species is linearly dependent on the respective concentrations, suggesting potential application in sulfite determination.
Keywords: Iron phenanthrolines; Modified electrodes; Sulfite; Electrocatalysis; Polypyridyl ligands;

The polymeric complex, {[Cu(tmen)][Pt(CN)4]} n (tmen  = tetramethylethylenediamine) has been synthesized and characterized by elemental analysis, infrared spectroscopy, single-crystal structure analysis and by measurement of magnetic properties. Crystal structure revealed that one cyano group is terminal whereas three crystallographically different cyano groups of [Pt(CN)4]2− anions bridge Pt(II) and Cu(II) atoms to form a two-dimensional structure. Consequently, four different ν(C   N) absorption bands have been observed in the IR spectrum.The polymeric complex, {[Cu(tmen)][Pt(CN)4]} n (tmen  = tetramethylethylenediamine) has been synthesized and characterized by elemental analysis, infrared spectroscopy, single-crystal structure analysis and by measurement of magnetic properties. Four ν(C   N) absorption bands have been recorded in the infrared spectrum of this compound, what corresponds with four different types of cyano groups in the structure. Crystal structure revealed that one cyano group is terminal whereas three crystallographically different cyano groups of [Pt(CN)4]2− anions bridge Pt(II) and Cu(II) atoms to form a two-dimensional structure with a weak antiferromagnetic exchange coupling.
Keywords: Copper(II); Tetracyanoplatinate(II); Tetramethylethylenediamine; Crystal structure; Infrared spectrum; Antiferromagnet;

Synthesis, structure, and properties of a new manganese thioantimonate(III), [ Mn 2 ( phen ) ( Sb 2 III S 5 ) ] n by Xin Wang; Tian-Lu Sheng; Sheng-Min Hu; Rui-Biao Fu; Xin-Tao Wu (399-401).
A new manganese thioantimonate(III), [ Mn 2 ( phen ) ( Sb 2 III S 5 ) ] n (1) (phen = 1,10-phenanthroline), has been synthesized under hydrothermal reaction. X-ray single-crystal structural analysis reveals that 1 is a two-dimensional (2D) layer of (6,3) topology. 1 is a semiconductor and characterized by elemental analysis, EDS, XRD, DTA-TG measurements, and the magnetic property of 1 has been describedA new manganese thioantimonate(III), [ Mn 2 ( phen ) ( Sb 2 III S 5 ) ] n (1) (phen = 1,10-phenanthroline), has been synthesized under hydrothermal reaction. X-ray single-crystal structural analysis reveals that 1 is a two-dimensional (2D) layer of (6,3) topology. Magnetism and thermal stability of 1 have also been investigated. Furthermore, 1 is a semiconductor with the band gap of E g  = 2.23 eV.
Keywords: Manganese; Thioantimonate(III); Multiple physical properties; Thermoanalysis; Semiconductor; Magnetism;

Initial use of 1,1′-oxalyldiimidazole for inorganic synthesis: Decomposition of the ligand as a means to the preparation of an imidazole- and oxalate(-2)-containing, 1D copper(II) complex by Theocharis C. Stamatatos; Spyros P. Perlepes; Catherine P. Raptopoulou; Vassilis Psycharis; Costas S. Patrickios; Anastasios J. Tasiopoulos; Athanassios K. Boudalis (402-405).
The CuII-assisted hydrolytic decomposition of 1,1′-oxalyldiimidazole yields the shown 1D coordination polymer, which contains both the decomposition “fragments” of the initially used ligand.The use of 1,1′-oxalyldiimidazole, (im)COCO(im), for the synthesis of coordination complexes is explored for the first time. The [Cu2(O2CMe)4(H2O)2]/(im)COCO(im) reaction system in 96% EtOH yields the new, 1D coordination polymer [Cu(ox)(Him)2] n (1), where Him is the neutral imidazole and ox2− is the oxalate(-2) ligand. A mechanism for the hydrolytic decomposition of the ligand is proposed. Complex 1 comprises neutral, zigzag chains with the η 1:η 1:η 1:η 1:μ (2.1111 using Harris notation) ox2− ligand bridging two neighboring CuII centers; two cis Him groups complete a Jahn–Teller distorted octahedral geometry at the metal. The dc, variable-temperature magnetic susceptibility data for the complex reveal antiferromagnetic CuII⋯CuII exchange interactions.
Keywords: Coordination polymer; Copper; Imidazole complex; Oxalate-bridged copper(II) complex; 1,1′-Oxalyldiimidazole;

A new dual luminescent pillared cerium(IV)sulfate–diphosphonate by Ferdinando Costantino; Pier Luigi Gentili; Nathalie Audebrand (406-408).
A new luminescent pillared Cerium sulfate–aminodiphosphonate has been prepared and its structure was solved ab initio from X-ray powder diffraction data.The inorganic layers are pillared from the bispipiredine groups belonging to the diphosphonic groups, alternating with the sulfate tetrahedra.A new pillared cerium(IV) sulfate–diphosphonate with formula Ce2(2H2O)[(O3PCH2)–NC10H18N–(CH2PO3)(SO4)2] · 6H2O has been hydrothermally synthesized and its structure has been solved ab initio from laboratory X-ray powder diffraction data.The luminescent and thermal properties of this compound have been preliminarily studied and the encouraging results place it in the field of functional hybrid materials.
Keywords: Lanthanides; Cerium phosphonates; X-ray powder diffraction; Luminescence;

The metathesis reaction of yttrium(III) halides with alkali metal phosphanides usually give no pure products. Here we present dinuclear [(thf)3YCl2{μ-P(H)Mes}]2 which forms regardless of the applied stoichiometry of KP(H)Mes and YCl3 in THF.The metathesis reaction of KP(H)Mes with YCl3 in tetrahydrofuran yields dinuclear [(thf)3YCl2{μ-P(H)Mes}]2 (1) with a yield of 26% (Mes = mesityl, C6H2-2,4,6-Me3). The seven-coordinate yttrium atoms exhibit pentagonal bipyramidal coordination spheres with bridging mesitylphosphanide substituents. The Y2PC fragments are nearly planar with an average Y–P bond length of 296.0 pm. The P-bound hydrogen atoms are perpendicular to these planes. The small 1 J(P,H) coupling constant of 125 Hz is in agreement with the picture that the H atom binds mainly to the p-orbital of the phosphorus atom.
Keywords: Yttrium; Metathesis reactions; Phosphanides; Salt elimination; Ligand exchange;

Homoleptic manganese(II)–azide layer: Synthesis, structural characterization and magnetic properties by Yu Ma; Ai-Ling Cheng; Wei-Wei Sun; Jiang-Yong Zhang; En-Qing Gao (412-416).
A novel compound in which two-dimensional homoleptic Mn(II) coordination layers with single μ 1,3-azide bridges host the organic methylviologen dications was synthesized and magnetically characterized.A host–guest compound {(MV)[Mn(N3)4]} n (1), where MV2+ (methylviologen dication) is generated in situ through the decarboxylation of 4,4′-dipyridinio-N,N′-diacetate, has been synthesized and characterized by X-ray crystallography and magnetic measurements. This is the first homoleptic two-dimensional Mn–azide compound, which contains single μ 1,3-azide bridged Mn(II) square layers with the organic MV2+ cations intercalated between the inorganic layers. Magnetic studies show antiferromagnetic interactions between adjacent metal ions (J  = −4.4 cm−1), and the symmetric feature of the structure precludes the possibility of spin canting in this compound.
Keywords: Azides; Manganese; Methylviologen dication; Homoleptic compound; Magnetism;

A novel heterostranded double-helix constructs a chiral channel which further develops into a homochiral helical two-dimensional sheet, and such a coordination polymer emits blue fluorescence.A novel heterostranded double-helical coordination polymer is self-assembly from two flexible ligands, 4-carboxymethylbenzoic acid (H2L) and 1,1′-(1,4-butanediyl)bis(imidazole) (abbr. as bbi), with Zn2+ ion under solvent-thermal condition. The heterostranded double-helix constructs a chiral channel, which is filled by lattice water molecules; the adjacent heterostranded double-helical channels share Zn2+ ions to develop into a homochiral helical two-dimensional sheet, and the right- and left-handed chiral sheets further array in an alternating fashion to generate a racemic crystal via van de Waals forces. This coordination polymer emits blue fluorescence in the solid state.
Keywords: 4-Carboxymethylbenzoic acid; 1,1′-(1,4-Butanediyl)bis(imidazole); Coordination polymer; Heterostranded double-helix; Blue fluorescence;

The complexes {[Cu(DPA)(μ1,5-dca)]ClO4} n (1), [Cu2(pic)21,3-H2NCO–N–CN)2(H2O)2] · 2H2O (2) and Cu(pic)2  · H2O (3) were isolated from the aqueous reaction of Cu(ClO4)2, 2-pyridyl-carbonyl-N,N-bis(2-pyridylmethyl)amine (DPA-CO-py) and sodium dicyanamide (Nadca). These were obtained via the hydrolysis of DPA-CO-py and dca promoted by Cu2+ ion.The reaction of Cu(ClO4)2, 2-pyridylcarbonyl-N,N-bis(2-pyridylmethyl)amine (DPA-CO-py) and sodium dicyanamide (Nadca) in aqueous medium led to the isolation of three complexes: {[Cu(DPA)(μ1,5-dca)]ClO4} n (1), [Cu2(pic)21,3-H2NCO–N–CN)2(H2O)2] · 2H2O (2) and Cu(pic)2  · H2O (3). The Cu2+ ion, during its complex formation with DPA-CO-py and dca not only assisted the hydrolysis of DPA-CO-py to the corresponding di(2-methylpyridyl)amine (DPA) and picolinic acid (Hpic) but also resulted in partial hydrolysis of one of the two nitrile groups of the dicyanamide, NC–N–CN (dca) to amidocynamide, H2NCO–NH–CN. The complexes were structurally characterized and the single X-ray structures for 1 and 2 reveal their identity. Complex 1 forms a 1D polymeric chain with the dca acting as a μ1,5-bridging ligand via the terminal nitrile nitrogen atoms. A distorted SP geometry around the Cu2+ centers was achieved by the three N-atoms of the DPA and by the two nitrile groups of the bridging dca ligands. Complex 2 consists of a dimeric unit with CuN3O2 chromophore in coordination polyhedron that has a distorted SP geometry. The amidocyanamide ion, H2NCO–N–CN acts as bis(monodentate) μ1,3-bridging ligand via the central amido and terminal nitrile nitrogen atoms whereas the picolinate anion forms a six-membered chelate ring through its pyridyl nitrogen and an oxygen atom of the carboxylate group, and the aqua water occupies the apical position of the structure. Complex 1 exhibits very weak antiferromagnetic coupling (J  = −0.31 cm−1) whereas 2 shows a significant antiferromagnetic interaction between the two copper centers (J  = −13.6 cm−1).
Keywords: Crystal structure; Magnetic properties; Copper; Bridged dicyanamide; Polynuclear complexes;

A solvothermally synthesized metal-organic framework in which neodymium(III)-formate layers are supported by m-phenylenediacrylate displays an unprecedented net topology and the magnetic properties are typical of the 4 I 9/2 state perturbed by ligand field and antiferromagnetic coupling.A new lanthanide(III) coordination polymer with mixed m-phenylenediacrylate (mpda) and formate bridges, [Nd(mpda)(HCOO)(H2O)] n was synthesized by a solvothermal reaction involving the in situ formation of formate from N,N-dimethyl formamide. The three-dimensional metal-organic framework contains μ3-formate-bridged Nd(III) layers pillared by the mpda ligand and exhibits an unprecedented 3,7-connected topology with Schläfli symbol (4,62)2(42,6)(47,64,810). The magnetic properties are typical of the Nd(III) 4 I 9/2 ground state perturbed by ligand field and probable antiferromagnetic exchange through triple μ2-oxygen bridges.
Keywords: Lanthanide; Coordination polymer; Solvothermal synthesis; Magnetic properties;

The open-chain crown ether assumes a half-ring shape with its four O atoms from two chains, and the separation angle between the two chelate chains adjusts according to the metal ionic radii.A new coumarin-based podand-type ligand (L) and its five complexes [Ln(NO3)3 L] (Ln = Pr (1), Eu (2), Gd (3), Tb (4) and Er (5)) were synthesized. The X-ray single-crystal diffraction analyses indicate that these complexes are isomorphous and lanthanide ions are ten-coordinated. The tetradentate ligand forms a half-ring coordination structure with its oxygen atoms and the distances of its two chelate chains vary regularly with the ionic radii. The photoluminescence properties were also investigated by phosphorescence, quantum yields and lifetime.
Keywords: Lanthanide contraction; Lanthanide complexes; Coumarin derivative; Crystal structures; Photoluminescence properties;

A novel chelate-assisted C–C bond formation during template condensation of 2-pyridinecarboxaldehyde and bis(3-aminopropyl)(2-aminoethyl) amine, ppe, in the presence of Cd(II) metal ion is reported.Cadmium(II) complexes of some potentially heptadentate tripodal Schiff base ligands with the general formula N{(CH2) n N=CHC5H4N}2{(CH2) m N=CHC5H4N}) (where n  =  m  = 2, L222; n  = 2, m  = 3, L322; n  = 3, m  = 2, L332) have been studied. These ligands are products of the full condensation of a number of tripodal tetraamines with 2-pyridinecarboxaldehyde. An unusual reaction of an additional 2-pyridine-carboxaldehyde with a methylene group adjacent to the imine bond only during template preparation of [Cd(L332)]2+ was observed. The latter reaction is a novel chelate-assisted C−C bond formation because it is occurred only where a rigid five-membered chelate ring is present.
Keywords: Schiff base; Heptadentate; Tripodal; Cadmium; Chelate-assisted;

Photoluminescent metal–organic coordination polymer incorporating one-dimensional silver chains by Geng-Geng Luo; Di Sun; Qin-Juan. Xu; Na Zhang; Rong-Bin Huang; LiRong Lin; Lan-Sun Zheng (436-439).
Solution phase reaction of AgNO3 with a mixture of benzene-1,3,5-tricarboxylate (H3BTC) and heterocyclic 2-aminopyrimidine (APYM) under the ammoniac conditions gives rise to a novel metal–organic polymer Ag3(BTC)(APYM)2, which possesses a unique 3D framework with 1D porous channels surrounded by carboxylato-supported Ag–Ag dimers, Ag–Ag chains, fully deprotonated [BTC]3− and APYM ligands. Furthermore, this metal–organic polymer exhibits strong blue photoluminescence maximized at 464 nm upon 383 nm excitation at room temperature. And upon cooling to 77 K, the emission spectrum seems narrowly red-shifted.Solution phase reaction of AgNO3 with a mixture of benzene-1,3,5-tricarboxylic acid (H3BTC) and heterocyclic 2-aminopyrimidine (APYM) under the ammoniacal conditions gives rise to a novel metal–organic coordination polymer Ag3(BTC)(APYM)2 (1). The structure of 1 possesses a unique three-dimensional (3D) framework with one-dimensional channels surrounded by carboxylato-supported Ag–Ag dimers, Ag–Ag chains, fully deprotonated [BTC]3− and APYM ligands. Moreover, 1 exhibits strong blue photoluminescence maximized at 464 nm at room temperature (λ ex  = 383 nm) and upon cooling to 77 K, the emission spectrum seems narrowly red-shifted.
Keywords: Silver(I); 2-Aminopyrimidine; Benzene-1,3,5-tricarboxylic acid; Metal–organic coordination polymer; Crystal structure; Ag⋯Ag interactions; Photoluminescence;

Complexes of 1,5-diselena[5]ferrocenophane (L) with silver(I) and mercury(II) have been prepared and characterised. Electrochemical studies showed that no electronic communication between ferrocenylene groups was observed in the silver complex [AgL 2]+, with the through-bond Fe⋯Fe distances out of the threshold for communication.The silver(I) and mercury(II) complexes of 1,5-diselena[5]ferrocenophane (L) have been synthesized. The X-ray crystal structures of L, [AgL 2]PF6 and [HgI2 L] are reported. The small cavity of the macrocyclic ligand means that the ring must undergo a conformational change to allow coordination, and there is no significant through-space interaction M⋯Fe in any of the complexes. Electrochemical studies showed that no electronic communication between ferrocenylene groups was observed in the silver complex where the through-bond Fe···Fe distances are in the range 13.10 (3)–13.27(3) Å.
Keywords: 1,5-diselena[5]ferrocenophane; Silver; Mercury; Electrochemistry;

Three polymeric zinc(II) complexes, derived from the end-on azide (μ1,1-N3) and end-to-end azide (μ1,3-N3) bridges and similar tridentate Schiff base ligands, have been synthesized and structurally characterized. The slight difference of the steric effects of the Schiff bases and the hydrogen bonds can influence the bridging modes of the azide groups. The urease inhibitory activities of the complexes were evaluated.Three polymeric zinc(II) complexes, derived from the end-on azide (μ1,1-N3) and end-to-end azide (μ1,3-N3) bridges and similar tridentate Schiff base ligands, have been synthesized and structurally characterized. The zinc(II) atom in each complex is in a midway between trigonal–bipyramidal and square–pyramidal coordination. The slight difference of the steric effects of the Schiff bases and the hydrogen bonds can influence the bridging modes of the azide groups.
Keywords: Synthesis; Schiff base; Zinc; Azide; Crystal structure;