Inorganic Chemistry Communications (v.12, #9)

Contents List (iii-xi).

A bimetallic 4f–3d tetranuclear complex was synthesized via hydrothermal reaction and structurally characterized. The complex is characteristic of a tetranuclear Gd2Zn2 structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. Photoluminescent investigation shows that the title complex displays an emission in ultraviolet region. Optical absorption spectra reveal the presence of a sharp optical gap of 3.66 eV.A bimetallic 4f–3d tetranuclear complex {[Gd(H2O)4(μ 2-C6NO2H5)2Gd(H2O)4](μ 3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd2Zn2 structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H2O)4(μ 2-C6NO2H5)2Gd(H2O)4](μ 3-C6NO2H4)2(ZnCl3)2} link to isolated chlorine ions and water molecules via π⋯π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.
Keywords: Crystal structure; Gadolinium; Lanthanide; Isonicotinic acid; Zinc;

Zinc(II) complex of terpyridine-crown macrocycle: A new motif in fluorescence sensing of zwitterionic amino acids by Hoi-Lun Kwong; Wing-Leung Wong; Chi-Sing Lee; Chi-Tung Yeung; Pang-Fei Teng (815-818).
A new fluorescence macrocyclic receptor based on the Zn(II) complex of a C 2-terpyridine and a crown ether has been developed for molecular recognition of zwitterionic amino acids in water/DMF solution.A new fluorescence macrocyclic receptor based on the Zn(II) complex of a C 2-terpyridine and a crown ether has been developed for molecular recognition of zwitterionic amino acids in water/DMF solution with remarkable selectivity towards l-aspartate ( K  = 4.5 × 104  M−1) and l-cysteine ( K  = 2.5 × 104  M−1).
Keywords: Zinc terpyridine; Crown-macrocycle; Fluorescence sensing; Amino acids sensing;

Tungsten-mediated synthesis of triazafluorenes by Janusz Szklarzewicz; Dariusz Matoga; Magdalena Owcarz; Wojciech Przybylski; Daisuke Yoshioka; Masahiro Mikuriya (819-822).
Reaction of 2-pyridinecarboxaldehyde with aliphatic 1,2-diamines in aqueous/ethanolic solution mediated by [W(CN)4O2]4− affords the cationic disubstituted triazafluorenes in good yields. Single-crystal X-ray analysis of 4,9-bis(2-pyridyl)-4a,9a-dihydro-3H,9H-3,8a,9a-triazafluorenium hexafluorophosphate salt 1 reveals the formation of a novel heterocyclic tricycle. Plausible mechanism of triazafluorenes formation is discussed.Reaction of 2-pyridinecarboxaldehyde with aliphatic 1,2-diamines in aqueous/ethanolic solution mediated by [W(CN)4O2]4− affords the cationic disubstituted triazafluorenes in good yields. Single-crystal X-ray analysis of 4,9-bis(2-pyridyl)-4a,9a-dihydro-3H,9H-3,8a,9a-triazafluorenium hexafluorophosphate salt 1 reveals the formation of a novel heterocyclic tricycle, triaza analogue of fluorene. The identity and purity of the compounds have been verified with elemental analysis as well as IR, 1H and 13C NMR, UV–Vis, Raman and cyclic voltammetry measurements. Aliphatic 1,3- and 1,4-diamines as well as cycloaliphatic and aromatic ones are not reactive. The proposed pathway for the tungsten-mediated formation of triazafluorenes is discussed.
Keywords: Tungsten; Cyano complexes; Azafluorene; Triazafluorene; Picolinic aldehyde;

New zinc(II) complex 1 with three different ligands: acetyloacetonate, tri-tert-butoxysilanethiolate and neutral 2-isopropylimidazole has been obtained and characterized by X-ray diffraction. It is the first example of a mononuclear zinc(II) complex mimicking the active site of farnesyl transferase.New zinc(II) complex 1 with three different ligands: acetyloacetonate, tri-tert-butoxysilanethiolate and neutral 2-isopropylimidazole has been obtained and characterized by X-ray diffraction. It is the first example of a mononuclear zinc(II) complex mimicking the active site of farnesyl transferase. (2-Isopropylimidazole)bis(acetylacetonato)zinc(II) 2 is also described as an intermediate product of the reaction leading to the formation of 1.
Keywords: Zinc; S-ligands; N-ligands; O-ligands; Structure elucidation; Enzyme modelling;

Fluorescence studies of quantum dots and zinc tetraamino phthalocyanine conjugates by Jonathan Britton; Edith Antunes; Tebello Nyokong (828-831).
Chemical linking of CdTe Qds capped with mercapto propionic acid (MPA) to zinc tetraamino phthalocyanine (ZnTAPc) showed Förster resonance energy transfer (FRET).CdTe Qds capped with mercapto propionic acid (MPA) were covalently linked to zinc tetraamino phthalocyanine (ZnTAPc) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of the formation of an amide bond between ZnTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and a mixture of QDs and ZnTAPc (i.e. without chemical linking) showed Förster resonance energy transfer (FRET). ZnTAPc quenched the QDs emission, giving quenching constants in the order of 103  M−1.
Keywords: Zinc tetraamino phthalocyanine; Energy transfer; Fluorescence quenching; Quantum dots;

Careful analysis of the X-ray diffraction data of layered hydroxysalts shows that nickel hydroxynitrate crystallizes in 1H polytype and cobalt hydroxynitrate in 3R polytype.Layered hydroxysalts derive their crystal structure from mineral brucite. Nickel and cobalt based hydroxysalts with the composition M3(OH)4(NO3)2 crystallize in trigonal crystal system. On careful examination of the PXRD patterns, it is found that Ni3(OH)4(NO3)2 crystallizes in hexagonal crystal system while Co3(OH)4(NO3)2 crystallizes in rhombohedral crystal system. This clearly demonstrates that the crystal structures in layered hydroxysalts are mainly dictated by the nature of the cation occupying the preferential site within the layer.
Keywords: Layered compounds; Chemical synthesis; X-ray diffraction; Crystal structure; Polytypism;

Two rod-based 3-D lead(II) tetrafluoroterephthalate coordination frameworks with sra topology: Syntheses, structures, and properties by Sheng-Chun Chen; Zhi-Hui Zhang; Qun Chen; Hai-Bo Gao; Qi Liu; Ming-Yang He; Miao Du (835-838).
This work presents two novel 3-D lead(II) coordination frameworks with tetrafluoroterephthalate, exhibiting sra type network structures based on infinite rod-shaped building units.Two three-dimensional (3-D) PbII coordination frameworks [Pb(BDC-F4)(CH3OH)] n (1) and [Pb(BDC-F4)(DMF)(CH3OH)] n (2) have been prepared by the reactions of Pb(NO3)2 with a rigid dicarboxyl compound tetrafluoroterephthalic acid (H2BDC-F4) in different solvents. Single crystal X-ray diffraction reveals that both complexes show the unusual rod-based coordination networks with sra topology, although they crystallize in different space groups (C2/c and P 1 ¯ ). Their spectroscopic, thermal, and fluorescence properties have also been studied.
Keywords: Crystal structure; Metal–organic framework; PbII tetrafluoroterephthalate; Rod-based network; Photoluminescence;

A series of palladium (II) complexes bearing new amino-salicylaldimine ligands have been synthesized and structurally characterized. These palladium complexes showed the high catalytic activity for the Suzuki reaction of activated aryl chlorides with phenylboronic acid in DMF under air atmosphereA series of amino-salicylaldimine ligands, 5-R-3-morpholinomethyl-salicylaldimine (R = t-Bu, CH3, Br) have been synthesized and structurally analyzed. These tridentate ligands add to palladium (II) to give high yields of air-stable complexes that are characterized by IR, 1H NMR and elemental analysis. Crystal structure details of complex 1 are presented. These Pd (II) complexes with amino-salicylaldimine ligands are versatile and efficient Suzuki catalysts towards cross-coupling of a variety of aryl chlorides with phenylboronic acid using DMF as solvent.
Keywords: Suzuki coupling reactions; Amino-salicylaldimine; Palladium catalyst; Crystal structure;

Synthesis of a new class of cyclometallated ruthenium(II) complexes and their application in dye-sensitized solar cells by Takashi Funaki; Masatoshi Yanagida; Nobuko Onozawa-Komatsuzaki; Kazuyuki Kasuga; Yuji Kawanishi; Mitsuhiko Kurashige; Kazuhiro Sayama; Hideki Sugihara (842-845).
A new class of cyclometallated ruthenium(II) complexes, Ru(tctpy)(C^N)(NCS) (1, 2) where C^N = a bidentate cyclometallating ligand, was synthesized as sensitizers for light, especially in the near-IR region for dye-sensitized solar cells (DSCs). A DSC sensitized with 2 shows a 10% incident photon-to-current conversion efficiency (IPCE) at 900 nm.We synthesized a new class of cyclometallated ruthenium(II) complexes, Ru(tctpy)(C^N)(NCS) (1, 2), where C^N is a bidentate cyclometallating ligand such as 2-phenylpyridinato or 2-(4-(2-phenylethynyl)phenyl)pyridinato. Although these complexes exist as stereoisomers, the microwave synthetic technique yielded only one isomer. These compounds act as light sensitizers and have excellent light-harvesting properties, especially in the near-IR region. Therefore, they can be used in dye-sensitized solar cells (DSCs). A DSC sensitized with 2 shows a 10% incident photon-to-current conversion efficiency at 900 nm.
Keywords: Ruthenium(II) complex; Cyclometallating ligand; Dye-sensitized solar cell; Sensitizer;

Two novel macrocyclic polyselenaferrocenophanes, 1,5,9-triselena[9]ferrocenophane (1) and 1,5,9,21,25,29-hexaselena[9.9]ferrocenophane (2), have been prepared by an efficient route. Their structures and electrochemistry were studied.Two novel macrocyclic polyselenaferrocenophanes, 1,5,9-triselena[9]ferrocenophane (1) and 1,5,9,21,25,29-hexaselena[9.9]ferrocenophane (2), have been prepared by the reaction of 1,1’-bis(3-bromopropylseleno)ferrocene and Na2Se. The new compounds have been characterized by a range of spectroscopic and analytical techniques, including 1H, 13C NMR spectrometry and X-ray crystallography.
Keywords: Crystal structure; Electrochemistry; 1,5,9-Triselena[9]ferrocenophane; 1,5,9,21,25,29-Hexaselena[9.9]ferrocenophane;

A novel two-dimensional network formed by complexation of cucurbituril with cadmium ions by Xing Feng; Xiao-Jun Lu; Sai-Feng Xue; Yun-Qian Zhang; Zhu Tao; Qian-Jiang Zhu (849-852).
A novel of compound {3[Cd2(C36H36N24O12)]·10Cl·10(H2O)}·2Cl 39(H2O) (1) was prepared and characterized by X-ray single-crystal diffraction, It consists of complexes of cucurbituril and cadmium cations through ion-dipole interaction, and a novel two-dimensional network is formed by the complexation of cucurbituril and cadmium ions.The crystal structure of compound {3[Cd2(C36H36N24O12)]·10Cl·10(H2O)}·2Cl·39(H2O) (1) is reported. It consists of complexes of cucurbituril and cadmium cations formed through ion-dipole interactions, in which a novel two-dimensional network is created by the complexation of cucurbituril and cadmium ions. Binding constants determined from voltammetric data indicate that Cd2+ has a high binding affinity for Q[6] ( K Cd 2 + = 9.95 × 10 9 M - 2 by CV) and forms a 2:1 (M2+/Q[6]) complex.
Keywords: Cucurbituril; Cadmium ion; Complexation; Capsules; Two-dimensional network;

A new sandwich polyoxometalate based on Keggin-type monolacunary polyoxotungstoborate anion, [Zr(α-BW11O39)2]14− by Yujuan Niu; Bin Liu; Ganglin Xue; Huaiming Hu; Feng Fu; Jiwu Wang (853-855).
A new sandwich-type polyoxometalate, [Zr(α-BW11O39)2]14−, was obtained from a conventional synthesis method and their single-crystal structure was determined. The crystal structure represents the first example of crystal structure for the sandwich Keggin-type polyoxotungstoborate.A new sandwich-type polyoxometalate based on Keggin-type monolacunary anion, [Zr(α-BW11O39)2]14− was synthesized and characterized by IR spectroscopy, UV electronic spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction. This is the first report of crystal structure for the sandwich Keggin-type polyoxotungstoborate.
Keywords: Polyoxometalate; Boron; Zirconium; Sandwich-type;

Two novel Zn(II) coordination polymers based on trigonal ligand: 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine by Bao-Cheng Wang; Xiao-Li Chen; Huai-Ming Hu; Hong-Liang Yao; Gang-Lin Xue (856-859).
Two novel Zn(II) coordination polymers have been hydrothermally synthesized by pytpy and organic-acid mixed ligands, giving networks from 2D to 3D structures. Both complexes show strong fluorescence emission and possess great thermal stabilities.Two novel Zn(II) coordination polymers, [Zn5(pytpy)8(fum)4(H2O)4(OH)2] n  ·  n(CH3OH) · 2n(H2O) (1) and [Zn3(pytpy)4 (btc)2] n  · 2n(H2O) (2) (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine, H2fum = fumaric acid, H3btc = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized and structurally characterized. Complex 1 is a 2D layer structure, which is constructed from linear pentanuclear Zn(II) subunits interconnected via bidentate-bridging pytpy ligands and tridentate-bridging fum2− anions. Complex 2 is a 3D network structure, μ2-pytpy ligands link the layers based on the heart-like hexanuclear subunits to form the 3D network. Both complexes show strong fluorescence emission upon excitation at 310 nm in solid state. Additionally, these two complexes possess great thermal stabilities, especially for 2, the framework is stable up to 350 °C.
Keywords: Zinc; Coordination polymer; Crystal structure; 4′-(4-Pyridyl)-3,2′:6′,3″-terpyridine; Fluorescent property; Thermal stability;

A manganese diphosphonate Mn(hpedpH2)·3H2O, where edge-shared MnO6 octahedra are linked by CPO3 tetrahedra to form a ladder-like double chain is reported. The compound experiences a field-induced magnetic transition at low temperature.A manganese diphosphonate Mn(hpedpH2)·3H2O [hpedpH4  = 1-hydroxy-2-(2-pyridyl)ethylidene-1,1-diphosphonic acid] has been synthesized under hydrothermal conditions. It shows a ladder-like chain structure in which the edge-shared {MnO6} octahedral are linked by {CPO3} tetrahedral through corner-sharing. The magnetization measurements reveal that dominant antiferromagnetic interactions are mediated between the magnetic centers and the compound experiences a field-induced magnetic transition at low temperature.
Keywords: Manganese; Diphosphonate; Magnetic property; Ladder-like chain;

A new polyoxotungstate-based {W72V30} spherical cage by Yan Li; Yang-Guang Li; Zhi-Ming Zhang; Qiong Wu; En-Bo Wang (864-867).
A new {W72V30} spherical cage composed of 12 pentagonal {(W)W5} moieties and 30 [VO(H2O)]2+ linkers was obtained, representing the second member in the pentagonal {(W)W5}-based polyoxotungstate family.We report the {W72V30} composed of 12 pentagonal {(W)W5} units and 30 [VO(H2O)]2+ linkers. This compound was characterized by the elemental analysis, thermogravimetry, X-ray diffraction analysis, spectroscopic methods (IR, UV/Vis, Raman), XPS, EPR, magnetic measurements and BVS calculations. This is the second member in the pentagonal {(W)W5}-based polyoxotungstate family.
Keywords: Cage magnetism; Polyoxotungstate; Vanadium;

Dicarbonylruthenium(II) complexes of diphosphine ligands and their catalytic activity by Biswajit Deb; Bibek Jyoti Borah; Bhaskar Jyoti Sarmah; Babulal Das; Dipak Kumar Dutta (868-871).
The reaction of [Ru(CO)2Cl2] n with diphosphine(P-P) [Xantphos and DPEphos] ligands produces two new mononuclear complexes [Ru(CO)2Cl2(P-P)], which exhibit significant catalytic activity in transfer hydrogenation reaction.The hexa-coordinated chelate complexes of the type [Ru(CO)2Cl2(P-P)](1a,b) [where P-P = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene(a) and [bis(2-diphenylphosphinophenyl)ether(b)] have been synthesized by reacting the polymeric precursor [Ru(CO)2Cl2] n with the ligands in 1:1 molar ratio. The complexes 1a,b are characterized by elemental analyses, Mass, IR and NMR spectroscopy together with the single crystal X-ray structure determination of 1a. The compound 1a crystallizes in a monoclinic system with space group C2/c showing a slightly distorted octahedral geometry around the Ru centre. The complexes 1a and 1b are thermally stable up to 300 °C and exhibit high catalytic activity in transfer hydrogenation of aldehyde and ketones to corresponding alcohols. The complexes 1a and 1b show much higher catalytic activity for the hydrogenation of aldehyde than ketones. In general, the catalytic efficiency of 1b is higher compared with 1a.
Keywords: Carbonyl complexes; Ruthenium(II); Diphosphine; Transfer hydrogenation;

A new binuclear potassium (І) complex with a novel 1D infinite water chain containing (H2O)12 clusters by Enjun Gao; Yun Huang; Mingchang Zhu; Lei Wang; Fuchun Liu; Hongyan Liu; Shuang Ma; Qunzhi Shi; Ni Wang; Chunyue Shi (872-874).
(a) Ball-and-stick representations of the novel 1D chain containing water dodecamer comprising of two different hexamers in 1. (The atoms with “B” sign represent the symmetric atoms and the hydrogen-bonding interactions between oxygen atoms are indicated with dashed lines). (b) The Space-Filling style of the host framework in 1 and the pseudo-cage cavities in which the novel 1D water chain indwells.A novel 1D infinite water chain made of (H2O)12 clusters containing two different chair water hexamers is found in the binuclear coordination compound, [K2(L)2(phen)4]·6H2O (1) (where L = 2,2′-azanediyldibenzoic dianion, phen = 1,10′-phenanthroline), which has been synthesized and structurally characterized by single-crystal X-ray diffraction. The fluorescence spectrum and thermogravimetric analysis (TGA) of the title complex 1 have been also discussed.
Keywords: Potassium complex; 2,2′-Azanediyldibenzoic acid; Binuclear structure; Dodecameric water cluster; Fluorescence;

An unusual 3D complex showing 5,8-connected topology with encapsulated 8-connected octamolybdate polyoxoanions by Wenju Wang; Lin Xu; Guanggang Gao; Fengyan Li; Xizheng Liu; Li Liu (875-878).
An unprecedented inorganic–organic framework, containing octamolybdate polyoxoanions as 8-connected nodes, defines a new 5,8-connected topology and represents 8-fold interpenetrated srs (SrS2 ) topological Cu(I)-organic secondary network for the first time.An unprecedented inorganic–organic framework, containing octamolybdate polyoxoanions as 8-connected nodes, defines a new 5,8-connected topology and represents 8-fold interpenetrated srs (SrS2 ) topological Cu(I)-organic secondary network for the first time. While the free bipy ligand displays weak luminescence in the solid state at room temperature, this compound exhibits an intense yellow radiation emission maximum at λ  ≈ 567 nm upon excitation at λ  ≈ 365 nm.
Keywords: Polyoxometalate; Organic–inorganic hybrid; Octamolybdate; Topochemistry;

From Hirshfeld surfaces analyses it can be concluded that in [C6H12N5O]3[(PO4)Mo12O36]·6H2O the hydrogen bond interaction play a main role in the construction of the 3D architecture, especially the CH⋯O interaction overruns the classic NH⋯O, N⋯HO interactions; van der Waals force between the peripheral atoms of component units cannot be ignored.A new soluble organic–inorganic hybrid based on polyoxomolybdate, [C6H12N5O]3[(PO4)Mo12O36]·6H2O (1), has been successfully synthesized and characterized by using elemental analysis, IR, UV spectroscopies, 1H NMR technique, and single-crystal X-ray diffraction. According to the results of X-ray crystallography the anion [(PO4)Mo12O36]3− has a typical Keggin structure and the Mo–O distances of Mo–O–Mo bonds are alternately short and long in the polyoxoanion structure. Hirshfeld surface analyses, especially d norm surface and fingerprint plots, are used for decoding intermolecular interactions in the crystal network and contribution of component units for the construction of the 3D architecture. The results indicate that in 1 the hydrogen bond interaction play a main role in the construction of the 3D architecture, especially the CH⋯O interaction which overruns the classic NH⋯O, N⋯HO hydrogen bond interactions; van der Waals force between the peripheral atoms of component units cannot be ignored.
Keywords: Hirshfeld surface analysis; Crystal structure; Hydrogen bonds; Polyoxometalate; Morpholine;

Two novel isostructural 3D 4d–4f coordination polymers, LnAg(OX)(IN)2·H2O (Ln = Nd (1); Eu (2), OX = oxalic acid, IN = isonicotinic acid), were prepared under hydrothermal condition and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR, TGA and photoluminescence measurements.The self-assembly of isonicotinic acid with metal salts under hydrothermal conditions obtained two new 4d–4f coordination polymers, LnAg(OX)(IN)2·H2O (Ln = Nd (1); Eu (2), OX = oxalic acid, IN = isonicotinic acid). The 3D isostructural complexes 1 and 2 are constructed by the assembly of 2D layers, which are built by carboxylate groups of isonicotinic acid and oxalate ligands coordinating to metal centers, with 1D linear linkers completed by silver ions. Furthermore, the luminescent property of complex 2 was investigated.
Keywords: Hydrothermal synthesis; Isostructural; Ln/Ag heterometallic complexes; Luminescence;

Two Ru(II) carbonyl chloride complexes with pyridine-2,6-diimine have been prepared and demonstrated to be effective in the transfer hydrogenation (TH) of acetophenone by propan-2-ol.Two Ru(II) carbonyl chloride complexes with pyridine-2,6-diimine, (L)Ru(CO)Cl2 (L = 2,6-diacetylpyridinebis(2,4,6-trimethylanil), 1; L = 2,6-diacetylpyridinebis(2,6-diisopropylanil), 2) have been synthesized and characterized. The structure of compound 1 has been determined by X-ray crystallography, which show the distorted octahedral geometry around Ru(II). Complexes 1 and 2 have been proved to be active in the transfer hydrogenation of acetophenone by propan-2-ol.
Keywords: Ruthenium complex; Crystal structure; Transfer hydrogenation; Pyridine-2,6-diimine;

Unique direct synthesis of cyanide-bridged Fe2Cu2 molecular squares by destruction of sodium nitroprusside by Olesia V. Vreshch; Oksana V. Nesterova; Vladimir N. Kokozay; Brian W. Skelton; Carlos J. Gómez García; Julia Jezierska (890-894).
New [Fe2Cu2(bpy)6(μ-CN)4(NCS)2]2[Fe(CN)5(NO)](NCS)2·5H2O complex, that contains unique tetranuclear Fe 2 II Cu 2 II squares has been prepared using one-pot self-assembly reaction of copper powder, sodium nitroprusside, ammonium thiocyanate and 2,2′-bipyridine (bpy) in acetonitrile solution at ambient conditions of air and water. The synthetic and structural features, spectroscopic and magnetic properties are reported.The one-pot reaction of copper powder, sodium nitroprusside, ammonium thiocyanate and 2,2′-bipyridine (bpy) in acetonitrile solution at ambient conditions of air and water yields the novel heterometallic [Fe2Cu2(bpy)6(μ-CN)4(NCS)2]2[Fe(CN)5(NO)](NCS)2·5H2O complex 1, which has been structurally and magnetically characterized. The most prominent feature of this complex is the unique tetranuclear Fe 2 II Cu 2 II squares comprised [Cu(bpy)NCS]+ and [Fe(bpy)2]2+ corners with CN edges. The Cu⋯Cu and Fe⋯Fe separations are ∼6.72 and ∼7.73 Å, respectively. The variable-temperature magnetic susceptibility study revealed that a very weak antiferromagnetic coupling is active between Cu(II) centers (J CuCu  = −0.37 cm−1).
Keywords: Molecular squares; Nitroprusside anion; Copper(II);

A 3D Gd–Ag coordination polymer constructed from pyridine-3,5-dicarboxylic acid: Synthesis, crystal structure and magnetic properties by Guang-Xiang Liu; Xiao-Ming Ren; Heng Xu; Sadafumi Nishihara; Rong-Yi Huang (895-897).
A novel heterometallic coordination polymer, [AgGd(PDC)2]·2H2O (1) (H2PDC = pyridine-3,5-dicarboxylic acid), have been synthesized under hydrothermal conditions. Complex 1 features an unusual three-dimensional pillar-layered coordination frameworks constructed from two-dimensional layers and Ag(PDC) pillars.A novel heterometallic coordination polymer, [AgGd(PDC)2]·2H2O (1) (H2PDC = pyridine-3,5-dicarboxylic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 features an unusual three-dimensional network structure in which infinite gadolinium-carboxylate chains are linked by [Ag(PDC)2]3− metalloligands to form a mixed-metal coordination network. Moreover, the luminescent properties and magnetic properties of 1 have also been investigated.
Keywords: Heterometallic coordination polymer; Crystal structure; Luminescence; Magnetism;

Ditopic, flexible hydrazone-based building blocks with pendant 2,2′:6′,2′′-terpyridine metal-binding domains by Jonathon E. Beves; Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Silvia Schaffner (898-901).
The synthesis and characterization of three new bis(2,2′:6′,2′′-terpyridine) (tpy) ligands containing different hydrazone spacers between the metal-binding domains are reported, and their ability to act as bridging ligands has been illustrated by the formation of [(tpy)Ru(μ-1)Ru(tpy)]4+ where 1 is 1,4-benzenedicarbaldehyde bis(2,2′:6′,2′′-terpyridin-4′-ylhydrazone) . The single crystal structure of [(tpy)Ru(μ-1)Ru(tpy)][PF6]4·8MeCN is described.The synthesis and characterization of three new bis(2,2′:6′,2′-terpyridine) (tpy) ligands containing different hydrazone spacers between the metal-binding domains are described. Treatment of 1,4-benzenedicarbaldehyde bis(2,2′:6′,2′′-terpyridin-4′-ylhydrazone) (1) with [(tpy)RuCl3] in the presence of N-ethylmorpholine results in the formation of [(tpy)Ru(μ-1)Ru(tpy)]4+. Single crystal X-ray diffraction data for [(tpy)Ru(μ-1)Ru(tpy)][PF6]4·8MeCN confirm the ability of the hydrazone-based ligand to bridge two ruthenium(II) centres, providing proof-of-principle for the application of this class of flexible ligand in the design of coordination polymers.
Keywords: 2,2′:6′,2′′-Terpyridine; Hydrazone; Ruthenium; Bridging ligand; Structure;

The first polypseudo-rotaxane structure based on the Wells–Dawson polyoxometalate by Peng-peng Zhang; Ai-Xiang Tian; Jun Peng; Hai-Jun Pang; Jing-Quan Sha; Yuan Chen; Min Zhu; Yong-Hui Wang (902-904).
The first polypseudo -rotaxane structure based on the Wells–Dawson polyoxometalate was hydrothermally synthesized.A polyoxometalate-based compound, (bix)[Cu(bix)][Cu2(bix)2(P2W18O62)]·2H2O (1) (bix = 1,4-bis(imidazol-1-ylmethyl)benzene), was hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analysis, and single X-ray diffraction. Compound 1 exhibits the 1D + 1D polypseudo-rotaxane structure consists of two parts: the P2W18–Cu2–(bix)2 chain which contains 26-membered Cu2(bix)2 macrocycles and the 1D Cu-bix line. Remarkably, it represents the first polypseudo -rotaxane structure based on the Wells–Dawson polyoxometalate.
Keywords: Wells–Dawson polyoxometalate; Polypseudo-rotaxane; Hydrothermal synthesis;

Exploiting anionic and cationic interactions with a new emissive imine-based β-naphthol molecular probe by Luz Fernandes; Maxime Boucher; Javier Fernández-Lodeiro; Elisabete Oliveira; Cristina Nuñez; Hugo M. Santos; Jose Luis Capelo; Olalla Nieto Faza; Emilia Bértolo; Carlos Lodeiro (905-912).
A new emissive molecular probe derived from 1,7-bis(2′-formylphenyl)-1,4,7-trioxaheptane and 2-hydroxy-1-naphthaldehyde has been synthesized by a Schiff-base condensation method. Its sensor capability towards cations such as Cu2+, Zn2+, Cd2+ and Hg2+, and anions such as halides (F, Cl, Br and I) and CN was explored in DMSO solution. The geometry was optimized using Density Functional Theory (DFT). The probe showed remarkable selectivity for Cu2+ and interaction with the more basic anions CN and F.A new emissive molecular probe derived from 1,7-bis(2′-formylphenyl)-1,4,7-trioxaheptane and 2-hydroxy-1-naphthaldehyde has been synthesized by a Schiff-base condensation method. Its sensor capability towards cations such as Cu2+, Zn2+, Cd2+ and Hg2+, and anions such as halides (F, Cl, Br and I) and CN was explored in DMSO solution. The geometry was optimized using density functional theory (DFT). The probe showed remarkable selectivity for Cu2+ and interaction with the more basic anions CN and F.
Keywords: Molecular probe; β-naphthol emission; Anion; Density functional theory; DFT; Schiff-base;

C–Cl bond cleavage of CH2Cl2 by the zinc(II) complex [Zn(phen)L2 ] ( L = PhC ( S ) NP ( O ) ( O i Pr ) 2 - ) with the formation of [Zn(phen)LCl] and CH2[PhC(S)NP(O)(OiPr)2]2 by Damir A. Safin; Maria G. Babashkina; Axel Klein; Michael Bolte; Dmitriy B. Krivolapov; Igor A. Litvinov (913-915).
The reaction of [Zn(phen)L2] ( L = PhC ( S ) NP ( O ) ( O i Pr ) 2 - ) with CH2Cl2 leads to the formation of complex [Zn(phen)LCl] and S,S′-bis(benzimidothio-N-diisopropoxyphosphoryl)methane L–CH2–L in high yields. Using CHCl3 or CCl4 instead of CH2Cl2 does not lead to the formation of chlorine substituted products even under reflux conditions. The crystal structure of [Zn(phen)LCl] was elucidated by X-ray diffraction. The Zn(II) atom in the complex is in a distorted tetragonal-pyramidal ClN2OS environment. The structure is stabilized by the intermolecular hydrogen bonds of the type C–H⋯Cl–Zn π⋯π stacking interactions between the phenanthroline rings.The reaction of [Zn(phen)L2] ( L = PhC ( S ) NP ( O ) ( O i Pr ) 2 - ) with CH2Cl2 leads to the formation of complex [Zn(phen)LCl] and S,S′-bis(benzimidothio-N-diisopropoxyphosphoryl)methane L–CH2–L in high yields. Using CHCl3 or CCl4 instead of CH2Cl2 does not lead to the formation of chlorine substituted products even under reflux conditions. Compounds obtained were investigated by 1H and 31P{1H} NMR spectroscopy, and microanalysis. The crystal structure of [Zn(phen)LCl] was elucidated by X-ray diffraction. The Zn(II) atom in the complex is in a distorted tetragonal-pyramidal ClN2OS environment. The structure is stabilized by the intermolecular hydrogen bonds of the type C–H⋯Cl–Zn and π⋯π stacking interactions between the phenanthroline rings.
Keywords: Bond cleavage; Zn(II) complexes; Crystal structure; Phosphorylthiobenzamide; 1,10-Phenanthroline;

Synthesis, characterization and crystal structure of cis,mer-[ReH(CO)2{PPh(OMe)2}3] by Sandra Bolaño; Jorge Bravo; Jesús Castro; María del Carmen Marín; Soledad García-Fontán (916-918).
The dicarbonylhydride complex cis,mer-[ReH(CO)2{PPh(OMe)2}3] was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)2 in [ReH(CO)3(PPh2OCH2CH2OPPh2)], this complex was treated with PPh(OMe)2 under UV irradiation.The dicarbonylhydride complex cis,mer-[ReH(CO)2{PPh(OMe)2}3] (1) was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)2 in [ReH(CO)3(L)] (L = PPh2OCH2CH2OPPh2), this complex was treated with PPh(OMe)2 under UV irradiation. The complex 1 was characterized by IR, 1H and 31P{1H} NMR spectroscopy and by crystal structure determination. The spectroscopic features are consequent with the cis,mer configuration showed by the X-ray crystallographic analysis of the complex. The environment of the metal centre is a distorted octahedron.
Keywords: Rhenium(I); Hydride complexes; Carbonyl complexes; Phosphonite ligands;

The first ribbed functionalized tris-dioximate clathrochelates with inherent hydroxyl substituents: Synthesis, spectra and X-ray structure by Aleksei B. Burdukov; Mikhail A. Vershinin; Ilya V. Eltsov; Nataliya V. Pervukhina; Yan Z. Voloshin (919-922).
The controlled hydrolysis of the dichlorine-containing iron(II) clathrochelate FeBd2(Cl2Gm)3(BF)2 precursor afforded the hydroxy-containing clathrochelate derivatives with the hydroxyl substituent inherently bound to the ribbed chelate fragment of the macrobicyclic ligand.The X-ray structural data for the deprotonated clathrochelate anion showed strong delocalization of its negative charge into the clathrochelate framework.The controlled hydrolysis of the dichlorine-containing iron(II) clathrochelate FeBd2(Cl2Gm)(BF)2 precursor (where Bd2− and Cl2Gm2− are α-benzyldioxime and dichloroglyoxime dianions, respectively) afforded the hydroxy-containing clathrochelate derivatives with the hydroxyl substituent inherently bound to the ribbed chelate fragment of the macrobicyclic ligand. The triethylammonium and tetra-n-butylammonium salts of the clathrochelate [FeBd2(OClGm)(BF)2] anion have been characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–Vis, 57Fe Mössbauer and 1H, 13C{1H}, 11B and 19F NMR spectroscopies, and X-ray crystallography. The X-ray structural data for this deprotonated anion showed strong delocalization of its negative charge into the clathrochelate framework.
Keywords: Macrocyclic complexes; Iron(II); Clathrochelates; Ligand reactivity; X-ray crystallography;

Synthesis, crystal structures and photoluminescence properties of Sm-based enantiomeric pair by Xi-Li Li; Bo Xiao; Chun-Sen Liu; Shao-Ming Fang (923-925).
Novel Sm-based enantiomeric pair with chiral ligand have been initially synthesized and characterized by crystal structure analysis and spectroscopic methods. They are isostructural, while octacoordinate Sm(III) is situated in a distorted square antiprism (SA) geometrical environment. The investigations on photoluminescence properties reveal that they display deep-red luminescence characteristic of the Sm3+ . Novel Sm-based enantiomeric pair, generally formulated Sm(DBM)3L (L R,R in 1, L S,S in 2, DBM = dibenzoylmethanate) have been successfully prepared via the reaction of Sm(DBM)3·2H2O with chiral ligands L R,R (−)-4,5-pinene bipyridine and L S,S (+)-4,5-pinene bipyridine (Scheme 1), respectively. The crystal structure analysis of 1 and 2 reveal that they crystallize in chiral space group P21 of monoclinic system. The central Sm(III) ion is octacoordinate with six β-diketonate oxygen atoms and two chiral pinene bipyridine nitrogen atoms, forming a coordination polyhedron best described as the distorted square antiprism (SA). The CD spectra (Fig. S1) further confirm that 1 and 2 are enantiomers. The photoluminescence investigations of 1 and 2 demonstrate that they display deep-red luminescence characteristic of the Sm3+ .
Keywords: Enantiomeric pair; Photoluminescence; Chiral ligand; Crystal structure;

Solely μ1,1-azido-bridged heterometallic Cu 2 II Mn 2 III compound by Chun-Hua Ge; Ai-Li Cui; Hui-Zhong Kou (926-928).
A novel end-on azide-bridged Cu 2 II Mn 2 III tetranuclear complex exhibits high-spin ground state of S  = 5.Solely end-on azide-bridged bimetallic Cu(II)–Mn(III) tetranuclear compound [Mn(salophen)(H2O)]2[Cu2(N3)6]·4H2O shows strong ferromagnetic coupling, giving rise to a ground spin state of S  = 5.
Keywords: Crystal structure; Heterometallic complex; Azide bridge; Polynuclear; Magnetic properties;

A ferromagnetic linear trinuclear Ni(II)-Schiff base complex supported by phenoxo and cinnamato bridges by Pampa Mukherjee; Michael G.B. Drew; Vassilis Tangoulis; Marta Estrader; Carmen Diaz; Ashutosh Ghosh (929-932).
A new linear trinuclear nickel(II) complex, [Ni3(salme)2(OCn)4] (Hsalme = 2-[(3-methylamino-propylimino)-methyl]-phenol, OCn = cinnamate), showing a weak ferromagnetic coupling (J  = 1.8(1) cm−1) through phenoxo and a novel tridentate bridging mode (1κ2 OO′:2κO′) of the cinnamate ligand has been synthesized and structurally characterized by X-ray crystallography.A new linear trinuclear nickel(II) complex, [Ni3(salme)2(OCn)4] (Hsalme = 2-[(3-methylamino-propylimino)-methyl]-phenol, OCn = cinnamate), showing weak ferromagnetic coupling (J  = 1.8(1) cm−1) through phenoxo and a novel tridentate bridging mode (1κ2 OO′:2κO′) of the cinnamate ligand has been synthesized and structurally characterized by X-ray crystallography.
Keywords: Nickel(II); Schiff base; Bridging cinnamate; X-ray structure; Magnetic properties;

Two novel Cd(II) coordination frameworks based on a semirigid asymmetric ligand4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid have been prepared by hydrothermal reaction. Complex 1 exhibits a novel (3, 5)-connected 2D network structure. Complex 2 exhibits a novel 3D CdSO4 topology, which is formed from different dinuclear cadmium unit. In addition, complexes 1 and 2 both exhibit luminescent properties at room temperature.Two novel Cd(II) coordination frameworks based on a semirigid asymmetric ligand L and aromatic multi-carboxylate ligands, {[Cd2L(btc)(H2O)2]·5H2O} n (1) and [Cd2L2(bdc)] n (2) (L = (4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid, H3btc = 1,3,5-benzenetricarboxylic acid, H2bdc = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized, and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography. Due to various coordination modes and conformations of the semirigid asymmetric ligand, and carboxylate containing co-ligands, therefore, the two complexes exhibit structural and dimensional diversity. Complex 1 exhibits a novel 2D (3, 5)-connected network structure with (3·52)(32·53·64·7) topology. Complex 2 exhibits a novel 3D CdSO4 topology, which is formed from different dinuclear cadmium units. In addition, the photoluminescence properties of the free ligand L, and complexes 1 and 2 were studied in the solid state at room temperature.
Keywords: Coordination polymer; Analogue (pyridyl)imidazole derivative; Dinuclear cadmium units; Photoluminescence property;