Inorganic Chemistry Communications (v.10, #9)

Contents List (iii-xii).

Selective and sensitive recognition of hexafluorophosphate via an unusual equilibrium between a cationic square host and a PF 6 - guest by In Sung Chun; Sung Jin Moon; Young Mee Na; Young-A. Lee; Kyung Ho Yoo; Ok-Sang Jung (967-970).
The equilibrium of [Pd(Me4en)(Isoni)(PF6)1/4]4(PF6)3/[Pd(Me4en)(Isoni)]4(PF6)4 (Me4en =  N,N,N′,N′-tetramethylethylenediamine; Isoni = isonicotinate) has been monitored via electrostatic interactions and size effects between a cationic square host and a PF 6 - guest.Hyper-selective and -sensitive recognition of hexafluorophosphate via a rigid molecular square has been carried out in solution. The equilibrium of [Pd(Me4en)(Isoni)(PF6)1/4]4(PF6)3/[Pd(Me4en)(Isoni)]4(PF6)4 (Me4en =  N,N,N′,N′-tetramethylethylenediamine; Isoni = isonicotinate) has been monitored via a suitable combination of electrostatic interactions and size effects between a cationic square host and a PF 6 - guest.
Keywords: Anion recognition; Hexafluorophosphate; Host–guest chemistry; Palladium(II)-complex;

An eight-nuclear complex, {[Ni(tacn)2]5[Cr(CN)6]3}ClO4  · 18 · 5H2O (tacn = 1, 4, 7-triazacyclononane) has been synthesized and characterized structurally and magnetically. This complex consists of a 3D structure with 1D metal–water chains containing planar hexacyclic water rings.An eight-nuclear complex, {[Ni(tacn)2]5[Cr(CN)6]3}ClO4  · 18.5H2O (tacn = 1, 4, 7-triazacyclononane), connected by 18.5 water molecules has been synthesized and characterized structurally and exhibits weak ferromagnetic interactions. This complex consists of a 3D structure with 1D metal–water chain containing planar hexacyclic water rings.
Keywords: Crystal structure; Hydrogen bonding; Magnetic property; Water ring;

A novel Cd(II)/4-pya coordination polymer {[Cd(μ-Cl)(4-pya)(H2O)]2  · 4H2O} (1) (4-pya =  trans-4-pyridylacrylate) was prepared from reactions of CdCl2  · 2.5H2O with 4-Hpya (4-pya =  trans-4-pyridylacrylate) under the presence of NH3 in H2O solution. The molecular structure of 1 was characterized by elemental analysis, IR, and X-ray crystallography and their luminescent properties were studied.A novel Cd(II)/4-pya coordination polymer {[Cd(μ-Cl)(4-pya)(H2O)]2  · 4H2O} (1) (4-pya =  trans-4-pyridylacrylate) was synthesized and structurally characterized. Single-crystal X-ray diffraction revealed that 1 consists of a 2D (4, 4) network constructed from the 4-pya bridging ligand and the dimeric [Cd(μ-Cl)]2 cores, in which each six-coordinated Cd(II) ion adopts an octahedral coordination geometry. Each 2D layer is further stacked along the a axis through hydrogen bonding interactions to afford a 3D hydrogen-bound network. An infinite water chain is generated via hydrogen bonds into each resulting 1D channel. The luminescent properties of 1 in the solid state were investigated.
Keywords: Cadmium; trans-4-Pyridylacrylic acid; Crystal structure; Luminescence; Coordination polymer;

An unusual 3D three-fold parallel interpenetrating network self-assembled from the grid-containing 2D layer motifs by Jian-Qiang Liu; Yao-Yu Wang; Lu-Fang Ma; Fan Zhong; Xi-Rui Zeng; Wei-Ping Wu; Qi-Zhen Shi (979-982).
A novel three dimensional interpenetrating architecture that is obtained from the first time from the self-assembly of grid-containing 2D layer motifs, which revealed the flexible V-shaped dicarboxylic acid and rigid N-containing ligand can also construct interpenetrating network.The new complex {[Cu(dde)(bpe)] · H2O} n (1) (dde = 4,4′-dicarboxydiphenyl ether, bpe = 1,2-bis(4-pyridyl)ethene) has been synthesized and characterized. It exhibits a novel (2D → 3D) three-fold parallel interpenetrating architecture that is obtained for the first time from the self-assembly of grid-containing 2D (4, 4) layer motifs. The fluorescent property of 1 is discussed.
Keywords: Interpenetration; Copper(II) complex; Crystal structure; Luminescent property;

Stable mixed-valence octanickel (I/II) tris-naphthyridyldiamido complexes by Hasanov Hasan; Uan-Kang Tan; Gene-Hsiang Lee; Shie-Ming Peng (983-988).
Air stable collinear mixed-valence octanickel (I/II) complexes were synthesized and characterized.Stable Nickel(I) complexes are rare, however, air stable collinear octanickel (I/II) complexes (4), (5) and (6) have been synthesized successfully by using the novel multidentate ligand trisnaphthyridyldiamine (2, H2tnda). The physical properties and the X-ray single crystal structures of these metal complexes have been characterized. The structures exhibit their corresponding redox relationships and reveal that the nickel centers are arranged linearly through the helical coordination of four ligands (2).
Keywords: Helicate; Polynuclear metal complexes; Tris-naphthyridyldiamine; Metal–metal bonding;

New dicarbonyl-o-semiquinonato rhodium complexes by Michael P. Bubnov; Vladimir I. Nevodchikov; Georgy K. Fukin; Vladimir K. Cherkasov; Gleb A. Abakumov (989-992).
Two novel dicarbonyl-o-semiquinonato rhodium complexes were obtained. Analysis of structural features of four analogous complexes – derivatives of 3,6-di-tert-butyl-o-semiquinone – allows us to suppose that the absence of intermolecular polar interactions in a complex having no back-bonded substituents is one of the reasons for an unusual photomechanical effect – reversible bending of thread-like crystals under light and/or warm excitation.Two novel dicarbonyl rhodium complexes with 3,6-di-tert-butyl-o-semiquinones containing back bonded –OCH3 and –F substituents were synthesized and characterized. The number of analogous dicarbonyl-o-semiquinonato rhodium complexes is discussed from the viewpoint of the phenomenon of “bending crystals”.
Keywords: Dicarbonyl(semiquinonato)rhodium complexes; Photomechanical effect; Crystal packing;

A blue luminescent inorganic–organic hybrid with infinite [Cd33-OH)22-Cl)2] connectivity by Anjian Lan; Lei Han; Daqiang Yuan; Feilong Jiang; Maochun Hong (993-996).
A novel layered inorganic–organic hybrid polymer, [Cd33-OH)22-Cl)2L2(H2O)2] (HL = 4-aminocinnamic acid), with strong blue luminescence has been reported. Its particular arrangement of the Cd(II), Cl, and OH forming an infinite 1D inorganic connectivity with the chair-like Cd4Cl2(OH)2 features is a new example of mixed Cd–OH–Cl discrete compounds.A novel layered inorganic–organic hybrid polymer, [Cd33-OH)22-Cl)2L2(H2O)2] (HL = 4-aminocinnamic acid), with strong blue luminescence has been reported. Its particular arrangement of the Cd(II), Cl, and OH forming an infinite one-dimensional inorganic connectivity with the chair-like Cd4Cl2(OH)2 features is a new example of mixed Cd–OH–Cl discrete compounds.
Keywords: Inorganic–organic hybrid; 4-Aminocinnamate; Photoluminescence; Cadmium(II);

First hexanuclear manganese(II) μ6-Cl centered carboxylate anion: Synthesis, structure and magnetic properties by Mikhail A. Kiskin; Grygory G. Aleksandrov; Vladimir N. Ikorskii; Vladimir M. Novotortsev; Igor L. Eremenko (997-1000).
Unusual hexanuclear manganese(ll) pivalate anion [Mn66-Cl)(μ22-Piv)12] has been synthesized.Reaction of manganese(II) polymer [Mn5Cl(OH)(Piv)8(MeCN)(HPiv)(H2O)] n (1, HPiv is pivalic acid) and 2-benzoylpyridine (L) in MeCN produces the ionic complex [Mn3(Piv)5L2(MeCN)]+[Mn6Cl(Piv)12]  · MeCN (3) containing the unusual hexanuclear {Mn66-Cl)} anion. An analogous anion was also observed in the complex [Mn6Cl(Piv)12](NEt4)+  · 5MeCN (4) prepared by the reaction of the polymer [Mn(Piv)2(EtOH)] n (2) with NEt4Cl in MeCN. Complexes 3 and 4 were characterized by the X-ray diffraction and magnetic susceptibility.
Keywords: Manganese(II) complexes; Pivalate ligands; X-ray structure; Magnetic properties;

Heavy Grignard reagents of strontium and barium are much more reactive than the derivatives of the lighter homologues. Ether cleavage reactions yield oxygen-centered cages such as the title compound [((thf)2BaPh2)4  · (thf)BaO], which is shown in the scheme.The direct synthesis of activated strontium and barium with iodobenzene in THF yields the corresponding THF complexes of phenylstrontium and phenylbarium iodide, respectively, which dismutate into the homoleptic compounds MPh2 and MI2. Already at low temperatures ether cleavage reactions take place and from this reaction, the oxygen-centered cage [((thf)2BaPh2)4  · (thf)BaO] was isolated and its molecular structure determined.
Keywords: Strontium; Barium; Phenylstrontium iodide; Phenylbarium iodide; Diphenylbarium;

The first structurally characterised cyclotriphosphazene substituted with a sulfonamide nitrogen by Eric W. Ainscough; Andrew M. Brodie; Ross J. Davidson; Carl A. Otter (1005-1008).
The first structurally characterised example of a substituted cyclotriphosphazene in which a ring phosphorus has been substituted but the nitrogen atom of a sulfonamide moiety is reported.The reaction between two equivalents of N-(2-hydroxyphenyl)-p-toluenesulfonamide (H2sulf) and [N3P3(biph)2Cl2] (H2biph = 2,2′-biphenol) produces the compound bis(2,2′-biphenylato)bis(2-oxyphenyl)-p-toluenesulfonamide cyclotriphosphazene (H2L) containing two geminal Hsulf moieties. Further reaction of H2L in basic conditions results in the removal of the sulfonamide arm and the slow formation of a novel phosphazene containing the spirocyclic sulf moiety. When this occurs in the presence of [Pd(bpy)Cl2] the reaction is facile and the new complex [Pd(bpy)(sulf)] (2) is also formed. Compounds H2L, 1 and 2 have all been characterised by single crystal X-ray crystallography.
Keywords: Cyclotriphosphazene; N-(2-hydroxyphenyl)-p-toluenesulfonamide; Palladium; 2,2′-Bipyridine; X-ray structure;

Structure and anion-exchange of a three-dimensional Ag(I) metal–organic framework by Da-Yu Wu; Wei Huang; Chun-Ying Duan; Qing-Jin Meng (1009-1013).
A three-dimensional coordination polymer [Ag4(C12H12N6)3](ClO4)4(H2O)5 (1), was achieved via the self-assembly of AgClO4 with ligand 2,5-bis(pyrazinyl)-3,4-diaza-2,4-hexadiene (L1). The anion-exchange behavior was detected for the compound 1 and it was confirmed that anion-exchange could reversibly occur between ClO 4 - and PF 6 - .A coordination polymer [Ag4(C12H12N6)3](ClO4)4(H2O)4 (1), was achieved via the self-assembly of AgClO4 with ligand 2,5-bis(pyrazinyl)-3,4-diaza-2,4-hexadiene (L1). The structure of compound 1 is a 3D metal–organic framework that consists of the circular helicate Ag3 (L1)3 secondary building blocks (SBUs). Each Ag 3 L 3 1 is capped at its every exo-monodentate pyrazinyl terminal by the unusual hexa-coordinated Ag(I) centers. Being filled within the cavities, the ClO 4 - anions could be exchanged reversibly with PF 6 - in the solid state.
Keywords: Schiff-base ligand; Metal–organic framework; Crystal structure; Anion-exchange;

A novel di-bridged dicyanamide dinuclear copper(II) compound with the formula [Cu(dipm)(μ-dca)(H2O)(ClO4)]2  · 2EtOH has been synthesised and structurally characterised by XRD, IR, EPR and magnetic measurements; (dipm = bis(pyrimidin-2-yl)amine).A novel bis (end-to-end) bridged dicyanamide dinuclear copper(II) compound with the general formula [Cu(dipm)(μ-dca)(H2O)(ClO4)]2  · 2EtOH (in which dipm = bis(pyrimidin-2-yl)amine) has been synthesised and characterised by X-ray crystallography and infrared spectroscopy. In addition, EPR and magnetic measurements have been performed.The geometry around the copper(II) ion is distorted octahedral with the basal plane formed by the two nitrogen atoms of the dipm ligand and two nitrogen atoms of two end-to-end bridging dca anions. The Cu–N distances vary from 1.979(4) to 2.004(3) Å. The apical positions are occupied by an oxygen atom of a water ligand with a Cu–O distance of 2.216(3) Å and an oxygen atom of a perchlorate anion with a semi-coordinating distance of 2.89(1) Å, 2.950(7) Å. A hydrogen-bond interaction of the Watson–Crick type is observed between the amine N atom of a dipm ligand to a pyrimidyl N atom of a neighbouring dipm ligand with a N⋯N distance of 2.970(4) Å. Furthermore, medium to strong hydrogen bond interactions are present between oxygen atoms of the water molecule, perchlorate lattice anions and ethanol molecules.The magnetic interaction between the Cu–Cu atoms is weak antiferromagnetic with a singlet–triplet separation (J) of −4.3  cm−1.
Keywords: Crystal structure; Copper; Hydrogen bond; Dicyanamide; Dinuclear;

Assembly, structure and magnetic property of one cyano- and oxamidato-bridged mixed valence CuI/CuII complex by Shu-zhong Zhan; Jian-ge Wang; Yong-qin Song; Qi-ying Lv; You Song; Jia-yin Su; Wen-yuan Yan (1019-1022).
One new cyano- and oxamidato-bridged mixed valence CuI/CuII complex 1 [ Cu 2 II (oxdipn)Cu I (CN) 3 ] (oxdipn is the dianion of N,N′-bis(dipropylenetriamine) oxamide) has been synthesized and structurally determined. Complex 1 consists of a one-dimensional zigzag chain –CuI(CN)–CN–CuII-(oxdipn)-CuII–NC–CuI– with CuII and CuI atoms linked together by oxdipn ligand and cyanide. Magnetic calculation on complex 1 showed that the oxamidato bridge transmits antiferromagnetic interactions between the Cu(II) ions.One new cyano- and oxamidato-bridged mixed valence CuI/CuII complex 1 [ Cu 2 II (oxdipn)Cu I (CN) 3 ] (oxdipn is the dianion of N,N′-bis(dipropylenetriamine) oxamide) has been synthesized and structurally determined. Complex 1 consists of a one-dimensional zigzag chain –CuI(CN)–CN–CuII-(oxdipn)-CuII–NC–CuI– with CuII and CuI atoms linked together by oxdipn ligand and cyanide. Magnetic calculation on complex 1 showed that the oxamidato bridge transmits antiferromagnetic interactions between the Cu(II) ions.
Keywords: Cyanide; Mixed valence CuI/CuII complex; Magnetic property;

Oxo-linked diruthenium(III) complex with 2,2′-bipyridine in ortho-metalation by Heng-Yun Ye; Jing-Lin Chen; Zhong-Ning Chen (1023-1025).
Reaction of the oxo-centered triruthenium precursor [Ru3O(OAc)6(py)2(MeOH)](PF6) with excess 2,2′-bipyridine induced isolation of oxo-bridged Ru 2 III,III diruthenium complex with ortho-metalated 2,2′-bipyridine, which exhibits four reversible or quasi-reversible redox waves due to successive one-electron oxidation or reduction of the diruthenium centers.Oxo-bridged dinuclear ruthenium(III) complex [Ru2(μ-O){η2(N,N)-bpy}2{μ-η1(C),η2(N,N)-bpy}2](PF6)2 (1) with ortho-metalated 2,2′-bipyridine (bpy) was synthesized and characterized by X-ray crystallography. Electrochemical studies revealed that the Ru 2 III,III complex exhibits four reversible or quasi-reversible redox processes due to successive oxidation or reduction of the diruthenium centers.
Keywords: 2,2′-Bipyridine; ortho-Metalation; Redox properties; Ruthenium;

Two novel anion-directed Cu(II) double betaine coordination polymers with different open frameworks were synthesized and structurally characterized, both of which are constructed by inorganic copper-oxo chains [Cu33–OH)22–H2O)2] n containing unusual chair-like [Cu3O4] units.The reaction of double betaine ligand L1 (L1  = 1,3-bis(pyridinio-4-carboxylato)-propane) with Cu(ClO4)2 and Cu(NO3)2, respectively, afforded two novel anion-directed coordination polymers with different open frameworks. The structure of [Cu3(L1)2(OH)2(H2O)2](ClO4)4·2H2O 1 is a unique 3-D open-framework with large S-shape channels, while [Cu3(L1)2(OH)2(H2O)2](NO3)4·2H2O 2 has a 2-D tubular structure. There exist inorganic copper-oxo chains [Cu33–OH)22–H2O)2] n in both 1 and 2 as secondary building units, in which the [Cu3O4] cores exhibit a rarely observed chair-like configuration. The anion template of ClO 4 - and NO 3 - , and labile coordination orientation of L1 ligand prompt the formation of different polymeric networks in 1 and 2.
Keywords: Anion template; Coordination polymers; Crystal structure; Double betaine; Inorganic chain;

β-Diketones derived from cyclopentadienyl rhenium tricarbonyl by Teresa Cautivo; Fernando Godoy; A. Hugo Klahn; Gonzalo E. Buono-Core; Diego Sierra; Mauricio Fuentealba; M. Teresa Garland (1031-1034).
Three new cyrhetrenyl-1,3-diketones complexes 1ac have been synthesized and fully characterized. They exist predominantly as the enol tautomer, in solution. X-ray crystallography of 1b reveals asymmetric enolisation in the direction furthest form the cyrhetrenyl group.The acetyl complex (η 5–C5H4COCH3)Re(CO)3 reacts with KO t Bu and an excess of appropriate ester to provide cyrhetrenyl-β-diketones complexes (η 5–C5H4COCH2COR)Re(CO)3 (R = CF3, 1a; CH3, 1b; Ph, 1c). These new 1,3-diketones exist predominantly as enol tautomer, although a enol/keto mixture of approx. 10:1 is present in complexes 1bc, in chloroform-d solution. The complexes have been characterized by spectroscopic techniques IR, 1H and 13C NMR and mass spectrometry. X-ray crystallography of complex 1b shows that only the enol form occurs in the solid state. The O–C–C–C–O fragment of the molecule is planar with asymmetric enolisation in the direction furthest from the cyrhetrenyl group.
Keywords: Cyrhetrenyl-1,3-diketone; Rhenium; Organometallic ligand;

A novel dinucleating macrocyclic Zn(II)–Ni(II) complex bearing six- and five-coordinate sites was prepared by a stepwise method.A novel hetero-dinucleating macrocyclic Zn(II)–Ni(II) complex was prepared by a stepwise procedure. The prepared mono- and dinuclear macrocyclic complexes were characterized by elemental analysis, IR, NMR spectroscopies, and molar conductance measurements. Characterization results confirm the expected C 2 symmetry geometry for mononuclear macrocyclic zinc complex with trans disposed pyridyl ligands. In contrast, the X-ray crystal structure of the dinuclear macrocyclic Zn(II)–Ni(II) complex reveals a C 1 symmetry geometry so that, Zn(II) ion is located in six-coordination site with cis disposed pyridyl ligands and the penta-dentate compartment is occupied by Ni(II) ion in a square pyramidal geometry. The thermogravimetric analysis (DTA/TG) of binuclear complex is also investigated.
Keywords: Dicompartmental ligand; Hetero-dinuclear complex; Macrocyclic complex; Zn(II)–Ni(II) complex; Thermogravimetric analysis;

Novel molecular architecture constructed on the skeleton of salen and salophen containing Zn(II) 2,2′-bipyridyl by Lallan Mishra; Rishikesh Prajapati; Keisaku Kimura; Shogo Kobayashi (1040-1044).
Salen and salophen complexed with Zn(bpy)Ac2  · H2O are developed as a material of micrometers length.The complexes of Zn(II)2,2′-bipyridine diacetate with salen (LH2) and salophen (L′H2) have been characterized in which complex with L′H2 in DMSO has yielded a novel one-dimensional molecular architecture of micrometer length.
Keywords: Schiff bases; Zn(II)2,2′-bipyridyl diacetate; Powder XRD; Microstructure; One-dimensional architecture; Photoluminescence;

[Ru(3-pyridyl-4′-terpy)2]2+ as a metallo-ligand – Adding to the complexity of supramolecular polymers by Cécile M. Ollagnier; Deanne Nolan; Christopher M. Fitchett; Sylvia M. Draper (1045-1048).
The generation of a unique layered heterometallic polymeric network resulting from the reaction of [Ru(3-pyridyl-4′-terpy)2]2+ with a source of Ag(I).The spectroscopic characterisation and isolation of [M(3-pyridyl-4′-terpy)2]2+[M = Fe, Ru] has allowed for the use of these complexes as metallo-ligands. On reaction with Ag(I) the Ru(II) complex gives a heterometallic polymeric network consisting of a layered non-interpenetrating set of elongated nets based on a (6,3) net of unequal linkages.
Keywords: Metallo-ligand; Fe(II) and Ru(II) polyimines; Supramolecular coordination polymers;

Solvothermal synthesis and crystal structure of a luminescent 2D copper(I) coordination polymer with a (3,4)-connected net by Guang-Fei Liu; Wen-Hua Zhang; Yang Chen; Dong Liu; Jian-Ping Lang (1049-1053).
A novel 2D coordination polymer {[Cu(tpt)(MeCN)](ClO4)} (1) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine), was prepared by reactions of [Cu(MeCN)4](ClO4) and excess tpt under the solvothermal conditions. The molecular structure of 1 was characterized by elemental analysis, IR, and X-ray crystallography and its luminescent properties were studied.A novel copper(I) coordination polymer, {[Cu(tpt)(MeCN)](ClO4)} (1) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine), was synthesized by solvothermal synthesis method and structurally characterized. Single crystal X-ray diffraction showed that 1 consists of a 2D (3,4)-connected network with a unique (53)2(5482) topology. The luminescent properties of 1 in the solid state at ambient temperature were investigated.
Keywords: Copper; 2,4,6-Tris(4-pyridyl)-1,3,5-triazine; Solvothermal synthesis; Luminescence; Crystal structure;

A novel dimeric arsenotungstate based on tetravacant subunit, H2[{Cu(phen)}8(β-AsW8O31)2] · 2.5H2O (phen = 1,10-phenanthroline) 1, has been prepared by hydrothermal methods. The title compound represents the first arsenotungstate example based on tetravacant Keggin polyanions. Furthermore, the comparison of β - Asw 8 O 31 9 - with few known tetravacant blocks exhibits the variety of XW 8 O 31 n - family in synthesis methods and existent forms.A novel dimeric arsenotungstate based on tetravacant subunit, H2[{Cu(phen)}8(β-AsW8O31)2] · 2.5H2O (phen = 1,10-phenanthroline) 1, has been prepared by hydrothermal methods with moderate acidity and characterized by elemental analyses, IR (25–650 °C), EPR, XPS, TG–DTA, and single-crystal X-ray diffraction. The title compound represents the first arsenotungstate example based on tetravacant Keggin polyanions. Furthermore, the comparison of β - Asw 8 O 31 9 - with few known tetravacant blocks exhibits the variety of XW 8 O 31 n - family in synthesis methods and existent forms.
Keywords: Polyoxometalates; Keggin; Tetravacant; Arsenotungstate; Crystal structure;

Design, synthesis, crystal structure and photophysical studies of an emissive, terbium based sensor for zinc by Xue-Qin Song; Wei Dou; Wei-Sheng Liu; Jun-Na Yao; Yan-Ling Guo; Xiao-Liang Tang (1058-1062).
A new selective lanthanide luminescent sensor for Zn(II) as well as its supramolecular structure is described here. The participation of nitrogen atoms in binding with Zn(II) complexation helps in the release of fluorescence through efficient intramolecular energy transfer from the pyridyl group to the Tb(III) ion. Thus Tb  ·  L represents a new case of luminescence enhancement with Zn(II) ion. This finding may not only enlarge the arsenal for detecting Zn(II) ion, but also add new merits to the chemistry of salicylamide derivatives, which are usually used as the chromophore for the lanthanide luminescence and constituents for tunable supramolecular chemistry.The synthesis, crystal structure and photophysical studies of the probe complex Tb  ·  L are described. Tb  ·  L is a mononuclear complex with a 46-membered macrocyclic rings constructed by intermolecular hydrogen bond. The mononuclear complex Tb  ·  L shows Laporte-forbidden 5D4  →  7F J f–f transitions and exhibits strong green luminescence emission bands in the solid state at ambient temperature which is characteristic of terbium ion. New selective luminescent lanthanide chemosensor for Zn(II) ion based on Tb  ·  L is also described, suggesting host–guest complexation signaling transduction mechanism.
Keywords: Lanthanide complex; Crystal structure; Hydrogen bond; Lanthanide luminescent sensor;

Ladder-like metal diphosphonates exhibiting field-induced magnetic transitions by Zai-Chao Zhang; Song-Song Bao; Li-Min Zheng (1063-1066).
Two isomorphous metal phosphonates M(C4H11NO7P2) · H2O [M = Mn (1), Co (2)], where edge-shared MO6 octahedra are linked by CPO3 tetrahedra to form a ladderlike double chain, are reported in this paper. Both experience field-induced magnetic transitions low temperature.Two new isomorphous phosphonates M(ahbdpH2) · H2O [M = Mn (1), Co (2); ahbdpH4  = 4-amino-1-hydroxybutane-1,1-diphosphonic acid, C4H13NO7P2] have been hydrothermally synthesized. Both exhibit a ladder-like chain structure in which the edge-shared {MO6} octahedra are linked by {CPO3} tetrahedra through corner-sharing. The double chains are connected through extensive hydrogen bonds among amino groups, phosphonate oxygen atoms and lattice water molecules, hence generating a three-dimensional network. Magnetic measurements reveal that both experience field-induced magnetic transitions at low temperature.
Keywords: Manganese; Cobalt; Diphosphonate; Magnetic property; Chain structure; Spin ladder;

Hydrothermal synthesis, crystal structure and photoluminescent property of a novel 3-D [La2(C2O4)2(NO3)(OH)(H2O)] · 3H2O by Dao-Jun Zhang; Tian-You Song; Jing Shi; Wei-Rong Yin; Ping Zhang; Li Wang; Ying Wang; Kui-Rong Ma; Yong Fan; Jia-Ning Xu (1067-1069).
A novel 3D [La2(C2O4)2(NO3)(OH) (H2O)] · 3H2O 1 has been synthesized under hydrothermal conditions and characterized. The bridging modes of both nitrates and oxalates in compound 1 are uncommon. The most simplest ligands , oxalates and nitrates in the presence of nicotinate, have unexpectedly generated an unusual compound.A novel 3D [La2(C2O4)2(NO3) (OH)(H2O)] · 3H2O 1 has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR, TGA, X-ray powder diffraction, X-ray single crystal diffraction and photoluminescence. The bridging modes of both nitrates and oxalates in compound 1 are uncommon. We have unexpectedly generated an unusual compound by using the simplest ligands, oxalates and nitrates in the presence of nicotinate (HIN).
Keywords: Hydrothermal; Nicotinate; Oxalate; Photoluminescence;

Linked macrocyclic systems. Interaction of copper(I) with tris-ring N2S2-donor macrocycles and their single-ring analogues by Andrew M. Groth; Leonard F. Lindoy; George V. Meehan; Brian W. Skelton; Allan H. White (1070-1073).
The interaction of two tri-linked N2S2-donor macrocyclic ligands and two single-ring analogues with Cu(I) is reported. Corresponding complexes of type [Cu3L](PF6)3 and single ring derivatives of type [CuL]PF6 have been synthesised. The X-ray structure of one single ring derivative showed that the four macrocyclic donor atoms coordinate to the Cu(I) in a quasi-tetrahedral manner; similar metal coordination geometries are proposed for the remaining three complexes.The interaction of two tri-linked N2S2-donor macrocyclic ligands, 1 (R = H) and 2 (R = H), and their related single ring derivatives, 3 (R = H) and 4 (R = CH2C6H5), with copper(I) is reported. Solid 3:1 (metal:ligand) complexes of type [Cu3L](PF6)3 (L =  1 and 2, R = H) and single ring derivatives of type [CuL]PF6 (L =  3, R = H; L =  4, R = CH2C6H5) were isolated; the X-ray structure of [CuL]PF6 (L =  3, R = H) showed that the four macrocyclic donor atoms coordinate to the copper(I) in a quasi-tetrahedral manner (Cu–N 2.089, 2.096(4); Cu–S 2.239, 2.264(2) Å, X–Cu–Y 104.5(1)–115.4(1))°.
Keywords: Copper(I); S2N2-donor macrocycle; Trinucleating macrocycle; X-ray;

The synthesis, reactivity and 1H NMR investigation of the hydroxyborohydride anion by Tomasz Ruman; Anna Kuśnierz; Agata Jurkiewicz; Andrzej Leś; Wojciech Rode (1074-1078).
The presented high yield synthetic route providing hydroxyborohydride salts is fast and economic, making hydroxyborohydrides quite attractive reagents. The first 1H NMR spectrum of hydroxyborohydride shows a very unusual pattern of resonances from heteronuclear coupling of boron-hydride moiety. The calculated 11B- and 10B–H coupling constants are in very good agreement with experimental data, and confirm the hypothesis about the detection of the (BH3OH) anion as an individual species in solution.Hydroxyborohydride (sodium and potassium salts) were prepared by a one-pot method and the 1H NMR spectrum of sodium hydroxyborohydride was recorded for the first time. Based on an NMR experiment, hydroxyborohydride was found to be more reactive toward acetone carbonyl than borohydride. The calculated 11B- and 10B–H coupling constants are in very good agreement with experimental data, and support the hypothesis about the detection of the (BH3OH) anion as an individual species in solution.
Keywords: Boron; 1H NMR; Hydroxyborohydride; Reduction; Carbonyl compounds;

Reaction of in situ generated 4-(6-(pyridin-4-yl)pyridin-3-yl)phenol (pph) from 5-(4-bromophenyl)-2-(pyridin-4-yl)pyridine (bppy) by an aromatic nucleophilic substitution and copper nitrate in hydrothermal conditions led to the formation of a supramolecular framework.Reaction of in situ generated 4-(6-(pyridin-4-yl)pyridin-3-yl)phenol (pph) from 5-(4-bromophenyl)-2-(pyridin-4-yl)pyridine (bppy) by an aromatic nucleophilic substitution and copper nitrate in hydrothermal conditions led to the formation of a supramolecular framework, formulated as [Cu(pph)2]2MoO4  · 1/2H2O (1). Compound 1 represents a two-dimensional network based on intermolecular O–H⋯O hydrogen bonds, in which Cu(II) is reduced to Cu(I). The formation mechanism of the aromatic nucleophilic substitution was discussed.
Keywords: Aromatic nucleophilic substitution; Copper; Supramolecular framework;

Sulfamethoxazole reacts with Ph3PAuCl and AgCl to give [Ph3PAu(SMTZ-1H+)] (SMTZ-1H+  = sulfamethoxazolato anion) (1) and [Ag(SMTZ-1H+)] (2). The lattice of 1 contains single molecules with linear N–Au–P bonds. Compound 2 comprises a two-dimensional polymeric assembly of deprotonated SMTZ and silver ions. The microbiologic activities of 1 and 2 were determined related to free sulfamethoxazole.Sulfamethoxazole (SMTZ) reacts with Ph3PAuCl and AgCl in methanol/triethylamine to give [Ph3PAu(SMTZ-1H+)] (SMTZ-1H+  = sulfamethoxazolato anion) (1) and [Ag(SMTZ-1H+)] (2). While the lattice of 1 contains single molecules with linear N–Au–P bonds, compound 2 comprises a two-dimensional polymeric assembly of the deprotonated SMTZ ligand and silver ions, which are coordinated by one oxygen and three nitrogens in a distorted tetrahedral array. The microbiologic activities (Mueller–Hinton broth dilution tests) of 1 and 2 were determined in relation to free sulfamethoxazole.
Keywords: Sulfamethoxazole; Au and Ag complexes; Antimicrobial activity;

Inserting sulfur donor ligands in axial positions of an extended trinickel chain by F. Albert Cotton; Carlos A. Murillo; Qingsheng Wang (1088-1090).
The stoichiometric reaction of [Ni3(dpa)4(CH3CN)2](PF6)2 (1) with NaSPh in dichloromethane, affords the linear trinuclear complex Ni3(dpa)4(SPh)2 (2) in good yield and excellent purity (dpa is the anion of 2,2′-dipyridylamine). This compound represents the first extended metal atom chain (EMAC) with sulfur-containing axial ligands.The stoichiometric reaction of [Ni3(dpa)4(CH3CN)2](PF6)2 (1) with NaSPh in dichloromethane, affords the linear trinuclear complex Ni3(dpa)4(SPh)2 (2) in good yield and excellent purity (dpa is the anion of 2,2′-dipyridylamine). This compound represents the first extended metal atom chain (EMAC) with sulfur-containing axial ligands and was characterized by X-ray single-crystal diffraction, elemental analysis, ESI–MS, UV–vis spectrum and magnetic susceptibility measurements.
Keywords: Extended metal atom chains (EMACs); X-ray crystallography; Magnetic susceptibility; Trinickel complex; Sulfur donor ligand;

3,4,5-Trisbenzyloxy benzoic acid as a new photo-sensitizer for Tb3+ion by J.R. Reshmi; S. Biju; M.L.P. Reddy (1091-1094).
A novel and highly conjugated aromatic carboxylic acid, 3,4,5-trisbenzyloxy benzoic acid (TBBA) and the corresponding Tb3+ complex has been synthesized and characterized by various spectroscopic techniques. The room temperature photoluminescence spectrum of Tb3+ complex is composed of typical green emissions, assigned to transitions between the first excited state 5D4 to the 7F J (J  = 6, 5, 4, 3), with an excited state lifetime of 0.397 ms and a quantum yield of 1%.A novel and highly conjugated aromatic carboxylic acid, 3,4,5-trisbenzyloxy benzoic acid (TBBA) and the corresponding Tb3+ complex has been synthesized and characterized by various spectroscopic techniques. The room temperature photoluminescence spectrum of Tb3+ complex is composed of typical green emissions, assigned to transitions between the first excited state 5D4 to the 7F J (J  = 6, 5, 4, 3), with an excited state lifetime of 0.397 ms and a quantum yield of 1%.
Keywords: Tb3+; 3,4,5-Trisbenzyloxy benzoate complexes; Luminescence;

Synthesis, crystal structure and fluorescence of a new triazolated-bridged 2-D coordination polymer by Bing Liu; Zhi-Qiang Zhou; Xiu-Cheng Zhang; Xian-You Zhang (1095-1098).
In the 2-D coordination polymer [Zn(L)Cl] n (HL = 3-amino-1H-1,2,4-triazole) synthesized by diffusion method, L ligands link Zn2+ to form 6- and 16-membered rings. The interconnection of the two kinds of rings results in a 2-D network, which features a (4,82) topological network. Hydrogen bonds connect the neighboring plane-symmetry layers into a 3-D framework. The fluorescent with emission at 416 nm is assigned to LMCT.In the 2-D coordination polymer [Zn(L)Cl] n (HL = 3-amino-1H-1,2,4-triazole) synthesized by diffusion method, L ligands link Zn2+ to form 6- and 16-membered rings. The interconnection of the two kinds of rings results in a 2-D network, which features a (4,82) topological network. Hydrogen bonds connect the neighboring plane-symmetry layers into a 3-D framework. The fluorescence with emission at 416 nm is assigned to LMCT.
Keywords: Zn(II); Crystal structure; 1,2,4-Triazole; Fluorescence; Topology;

First μ 3-oxalato-bridged cis and trans configurations nickel macrocyclic complex: Synthesis, structure and magnetic properties by Hui Liu; Wen Gu; Gongfeng Xu; Yuhua Feng; Yingying Kou; Li Feng; Shiping Yan; Daizheng Liao; Peng Cheng (1099-1101).
A novel nickel macrocyclic complex has been synthesized. In the complex, oxalates contain two types of coordination environments: cis-bi-monodentate and cis-mono-bidentate. The cyclam adopts a folded conformation coordinating to Ni(II) atoms by the typical trans-III mode with the appropriate R, R, S, S arrangement and cis-V conformation with the R, R, R, R nitrogen configuration.A novel nickel macrocyclic complex {[Ni2(cyclam)2(μ 3-C2O4)]} n  · (ClO4)2  · H2O has been synthesized and structural characterized by single-crystal X-ray diffraction. The complex forms a chain-like one-dimensional structure linked through a novel μ 3-oxalato-bridging mode, which has never been reported for nickel. The complex adopts both trans-III configuration with the R, R, S, S arrangement of the four chiral nitrogen centers and cis-V conformation with the R, R, R, R nitrogen configuration. Variable-temperature magnetic susceptibility studies indicate the existence of weak antiferromagnetic (zj  = −1.07 cm−1) coupling.
Keywords: Nickel (II) complex; 1,4,8, 11-tetraazacyclotetradecane (cyclam); Oxalate; Magnetic studies;

One-pot reaction of S2O2-macrocyclic ligand L with AgClO4 together with 4,4′-bipyridine (bpy) afforded a unique dumbbell-shaped complex 1, [(AgL)2(μ-bpy)](ClO4)2.One-pot reaction of S2O2-macrocyclic ligand L with AgClO4 together with 4,4′-bipyridine (bpy) afforded a unique dumbbell-shaped complex 1, [(AgL)2(μ-bpy)](ClO4)2. The macrocyclic dinuclear silver(I) complex 1 was structurally characterized by X-ray crystallography and MALDI-TOF-MS spectrometry. The crystal structure of 1 shows the silver(I) in a distorted square pyramidal environment formed by two sulfur and two oxygen donors from L and one nitrogen donor from bpy. Comparative NMR studies suggest the existence of the complex 1 in solution.
Keywords: S2O2-macrocycle; 4,4′-Bipyridine; Silver(I) complex; Molecular dumbbell; Crystal structure;

Four-, six- and eight-coordinated lead(II) complexes with amine- or amide-type tripodal ligands by Donghyun Kang; Jai Young Lee; Ji-Eun Lee; So Young Lee; Kyu Seong Choi; Shim Sung Lee (1105-1108).
Three lead(II) complexes, [Pb(L 1)](ClO4)2 (1) (L 1  = tris(2-benzylaminoethyl)amine), [Pb(L 2)2](ClO4)2 (2) (L 2  = tris(4-phenyl-3-aza-2-oxobutyl)amine) and [Pb2(L 3)2](ClO4)4 (3) (L 3  = tris[3-aza-2-oxo-4-(2-pyridyl)butyl]amine) were synthesized. Complex 3 is a unique dinuclear 2:2 complex, in which two hexa-dentate lead(II) ions are linked by two carbonyl μ–O atoms forming a Pb2(μ–O)2 parallelogram-type moiety.Three novel lead(II) complexes, [Pb(L 1)](ClO4)2 (1) (L 1  = tris(2-benzylaminoethyl)amine), [Pb(L 2)2](ClO4)2 (2) (L 2  = tris(4-phenyl-3-aza-2-oxobutyl)amine) and [Pb2(L 3)2](ClO4)4 (3) (L 3  = tris[3-aza-2-oxo-4-(2-pyridyl)butyl]amine) were synthesized and structurally characterized. All three complexes show different stoichiometries as well as coordination numbers of four in 1, eight in 2 and six in 3, respectively. Complex 1 displays a typical tripodal-type 1:1 (M:L) structure and 2 shows a sandwich-type 1:2 structure. The octa-dentate lead(II) ion in 2 is at the center of a dicapped trigonal prism. Complex 3 is revealed as a unique dinuclear 2:2 complex, in which two hexa-dentate lead(II) ions are linked by two carbonyl μ–O atoms forming a Pb2(μ–O)2 parallelogram-type moiety.
Keywords: Tripodal ligand; Amine-type; Amide-type; Lead(II) complex; Crystal structure;

Hydrothermal synthesis, crystal structure, and thermal stability of a novel 3D cadmium phosphonate with double-stranded helical channels by Da-Peng Dong; Jing Li; Zhen-Gang Sun; Xue-Fang Zheng; Hui Chen; Lei Meng; Yan-Yu Zhu; Yan Zhao; Jing Zhang (1109-1112).
A novel 3D cadmium phosphonate, [enH2]0.5[Cd2(HL)(L)] 1 (H3L = 2-hydroxyphosphonoacetic acid; en = ethylenediamine) has been synthesized under hydrothermal reaction conditions. The structure of compound 1 comprises right-handed double-stranded helical channels, left-handed double-stranded helical channels and achiral channels that are connected through cadmium atoms and L3−ligands to form a meso compound, and the protonated ethylenediamine cations are located inside the achiral channels.In the presence of ethylenediamine template agents, a novel 3D cadmium phosphonate with double-stranded helical channels, [enH2]0.5[Cd2(HL)(L)] 1(H3L =  2-hydroxyphosphonoacetic acid; en = ethylenediamine) has been synthesized by hydrothermal reaction at 140 °C and characterized by single-crystal X-ray diffraction as well as by infrared spectroscopy, elemental and thermogravimetric analysis. The structure of compound 1 comprises right-handed double-stranded helical channels, left-handed double-stranded helical channels and achiral channels that are connected through cadmium atoms and L3−ligands to form a meso compound, and the protonated ethylenediamine cations are located inside the achiral channels.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Cadmium;

In this article, a Cu(I)-halide complex [Cu(II)Cu(I)3(1,10′-phen)Cl5] n (1) has been synthesized under hydrothermal reaction conditions. Complex 1 is a three-dimensional supramolecular network composed by one-dimensional chain-like structure. To our interest, in the chain, there exist Cu6Cl6 building unit, which is seldom found in Cu(I)-halide complex. Furthermore, the Cu6Cl6 building unit is extended by Cu(II)(1,10′-phen)Cl2 unit. Complex 1 exhibits strong luminescent property at room temperature.In this article, a Cu(I)-halide complex [Cu(II)Cu(I)3(1,10′-phen)Cl5] n (1) has been synthesized under hydrothermal reaction condition. Complex 1 is a three-dimensional supramolecular network composed by one-dimensional chains. To our interest, in the chain, there exists Cu6Cl6 building unit, which is seldom found in Cu(I)-halide complex. Furthermore, the Cu6Cl6 building unit is extended by Cu(II)(1,10′-phen)Cl2 unit. To our knowledge, this is the first mixed-valence Cu-halide complex composed from Cu6Cl6 building unit. Complex 1 exhibits strong luminescent property at room temperature.
Keywords: Mixed-valence Cu; Cu6Cl6 building unit; Hydrothermal reaction; Luminescent property;

Two azido-bridged coordination polymers were synthesized and structurally characterized. One is a 1D helical chain polymer with both azides as μ1,1-bridge which displaying wheel packing motif and strong ferromagnetic interaction. The other one shows 2D layer network in which an azide acts as μ1,1,3-bridge and the other azide as monodentate ligand.Two azido-bridged coordination polymers, [Ni(L)(μ1,1-N3)2] (1) and [Cu(L)(μ1,1,3-N3)(N3)] (2) (L = 1,2-diaminocyclohexane), have been synthesized and characterized by elemental analyses, IR spectra and X-ray structural analyses. Complex 1 is a one-dimensional helical chain coordination polymer with both azides as μ1,1-bridge, which exhibits interesting wheel motif. Complex 2 shows two-dimensional layer network in which an azide acts as μ1,1,3-bridge and the other azide as monodentate ligand. Cyclic voltammogram gives quasi-reversible redox wave of Cu(II)/Cu(I) pair. Variable-temperature magnetic property of 1 was investigated, which shown strong ferromagnetic interaction arising from the μ1,1-azido bridging nickel(II) chains.
Keywords: Azide; 1,2-Diaminocyclohexane; Coordination polymer; Crystal structure; Magnetic property;

Recrystallization of bis(acetylacetonato)nickel(II) from methanol solution yields turquoise colored needle-like crystals of bis(acetylacetonato)dimethanolnickel(II) which was isolated and fully characterized by 1H and 13C NMR, FT-IR spectroscopy, and single crystal X-ray diffraction. The X-ray structure analysis gives essentially a triclinic unit cell of bis(acetylacetonato)dimethanolnickel(II) containing one centrosymmetric molecule of the formula Ni[(O2C5H7)2(OHCH3)2].Bis(acetylacetonato)dimethanolnickel(II) was isolated as turquoise needle-like crystals by recrystallization of bis(acetylacetonato)nickel(II) from methanol solution and fully characterized by 1H and 13C NMR, FT-IR spectroscopy, and single crystal X-ray diffraction. The X-ray structure analysis gives essentially a triclinic unit cell of bis(acetylacetonato)dimethanolnickel(II) containing one centrosymmetric molecule of the formula Ni[(O2C5H7)2(OHCH3)2]. The Ni(II) ion is located at the inversion centre of a tetragonally distorted octahedral coordination sphere. The equatorial plane of the tetragonally distorted octahedral coordination sphere includes four O-donor atoms of two acetylacetonato ligands and the axial positions are occupied by two oxygen atoms of two methanol ligands.
Keywords: Acetylacetonate; Methanol; Nickel; Bis(acetylacetonato)dimethanolnickel(II); Structure;