Inorganic Chemistry Communications (v.13, #3)

Contents List (iii-xi).

Synthesis and characterization of O-methyldithiocarbonate and triphenylphosphoniodithiocarboxylate complexes containing a tris(pyrazolyl)borato (Tp) ligand by Yih-Hsing Lo; Yih-Hsuan Fong; Hung-Chun Tong; Yao-Ren Liang; Ting-Shen Kuo; Chiung-Cheng Huang (331-333).
The CS2 insertion of ruthenium chloride complex Tp(PPh3)2Ru–Cl (1) in the presence of CH3OH resulted in the O-methyldithiocarbonate complex Tp(PPh3)Ru(κ2-S2COCH3) (3) and triphenylphosphoniodithiocarboxylate complex [Tp(PPh3)Ru(κ2-S2CPPh3)]Cl (4) with the zwitterion - S 2 CPPh 3 + as a chelating ligand depending on the reaction conditions.The O-methyldithiocarbonate and triphenylphosphoniodithiocarboxylate complexes having a Tp ligand (Tp = BH(pyrazol-1-yl)3) were prepared. The CS2 insertion of ruthenium chloride complex Tp(PPh3)2Ru–Cl (1) in the presence of CH3OH resulted in the O-methyldithiocarbonate complex Tp(PPh3)Ru(κ2-S2COCH3) (3) and triphenylphosphoniodithiocarboxylate complex [Tp(PPh3)Ru(κ2-S2CPPh3)]Cl (4) with the zwitterion - S 2 CPPh 3 + as a chelating ligand depending on the reaction conditions. Attractively, this outcome contrasts sharply with similar reaction of carbon disulfide with Cp(PPh3)2Ru–Cl, no reaction is observed, even under drastic, vigorous conditions. The structures of 3 and 4 have been determined by X-ray diffraction analysis.
Keywords: Tp; Ruthenium; Carbon disulfide; Triphenylphosphoniodithiocarboxylate; Zwitterion; O-methyldithiocarbonate;

Systematic synthesis of functional unsymmetric FeZn model complexes for plant purple acid phosphatases by Martin Jarenmark; Håkan Carlsson; Vladimir M. Trukhan; Matti Haukka; Sophie E. Canton; Monica Walczak; Wilfred Fullagar; Villy Sundström; Ebbe Nordlander (334-337).
The heterodinuclear complexes [FeZn(L)(CH3CO2)2]+ (L = ICIMP, IPCPMP) are structural models for the dinuclear active sites of plant purple acid phosphatases. They can be systematically synthesized from mononuclear iron complexes and are functional models that catalyze the transesterification of 2-hydroxypropyl p-nitrophenyl phosphate.The heterodinuclear complexes [FeZn(L)(CH3CO2)2]+ (L = ICIMP or IPCPMP) are structural models for the dinuclear active sites of plant purple acid phosphatases. They can be systematically synthesized from mononuclear iron complexes and enhance the rate of transesterification of 2-hydroxypropyl p-nitrophenyl phosphate, an assay for the catalytic hydrolysis performed by purple acid phosphatases.
Keywords: Bioinorganic chemistry; Heterodinuclear; Dinuclear; Purple acid phosphatase; Model complexes; Transesterification; HPNP; Iron; Zinc;

Three-dimensional fivefold interpenetrating microporous metal–organic framework based on mixed flexible ligands by Xiao-Ying Huang; Ke-Fen Yue; Jun-Cheng Jin; Jian-Qiang Liu; Cheng-Jun Wang; Yao-Yu Wang; Qi-Zhen Shi (338-341).
An novel diamondoidlike coordination polymer {[Cd(oba)(bib)]·2H2O} n (1) have been synthesized. Interestingly, the compound still exhibits significant void space that may be filled with guest H2O molecules in spite of the fivefold interpenetration that occurs in the solid. Besides, this compound also exhibits high thermal stability and blue-shift emission, and can be explored for potential blue luminescent materials.The chiral diamondoidlike Cd(II) containing coordination polymer {[Cd(oba)(bib)]·2H2O} n (1) (oba = 4,4′-oxybis(benzoate), bib = 1,4-bis(2-methyl-imidazol-1-yl)butane) is reported; the 3D networks interpenetrate fivefold, nevertheless leave cavities capable of including sizable guest molecules. This compound also exhibits high thermal stability and blue-shift emission, and can be explored for potential blue luminescent materials.
Keywords: Interpenetration; Microporous structure; Crystal engineering; Fluorescence spectrum;

Synthesis of an osmafuran from photochemical hydrolysis of OsCl2(CH=C(PPh3)C(O)-η2-CH=CH2)(PPh3)2 by Xu-Min He; Qixuan Liu; Lei Gong; Yumei Lin; Ting Bin Wen (342-345).
The η2-alkene coordinated α,β-unsaturated ketone complex 1 which is very stable even at elevated temperature can be converted to the corresponding osmafuran 2 almost quantitatively by ultraviolet irradiation. This new highly efficient method for the preparation of osmafurans via photochemically assisted hydrolysis of η2-α,β-unsaturated ketone complexes, presents an addition to previous synthetic approaches.The η2-alkene coordinated α,β-unsaturated ketone complex Os(CH=C(PPh3)C(O)-η2-CH=CH2)Cl2(PPh3)2 (3) is very stable even at elevated temperature due to the strong steric hindrance effect of PPh3 ligands. However, compound 3 in a chloroform solution can be almost quantitatively converted into the corresponding osmafuran [OsCl(CO)(PPh3)2(CHC(PPh3)C(CH3)O)]Cl (6) via hydrolysis of the η2-coordinated olefin under photochemical conditions. Osmafuran 6 has been characterized by single crystal X-ray diffraction analysis, NMR spectroscopy and elemental analysis data. The UV-induced reaction provides a new highly efficient method for preparation of osmafurans by hydrolysis of η2-α,β-unsaturated ketone complexes.
Keywords: Metallacycle; α,β-unsaturated ketone; Osmafuran; Ultraviolet radiation; Photochemical;

Three 12-MC-4 organotin(IV) complexes [12-MC[RSn(IV)]N(shi)-4] (R  = Et(1), Bu(2), Ph(3); Shi = salicylhydroxamic acid), which are the novel example of organotin(IV) metallacrowns, have been synthesized and characterized by elemental analyses, IR, TGA and X-ray diffraction.Three 12-metallacrown-4(12-MC-4) organotin(IV) complexes [12-MC[RSn(IV)]N(shi)-4] (R  = Et(1), Bu(2), Ph(3); Shi = salicylhydroxamic acid) have been synthesized and characterized by elemental analyses, IR, TGA and X-ray diffraction. Single-crystal X-ray analyses reveal that all the complexes 13 contain a neutral 12-membered metallacrown ring which is formed by the succession of four repeating units of –[Sn–N–O]–. The metallacrown molecules of complexes 1 and 2 are further linked by intermolecular C–H···O interactions to form a 2D supramolecular networks, while the molecules of complex 3 are linked by intermolecular C–H···O and C–H···π interactions to form a 3D framework.
Keywords: Metallacrown; Organotin(IV); Salicylhydroxamic acid; C–H···O/C–H···π interactions;

Selective metal complexes can be prepared from one pot reaction of 2,6-pyridinedicarboxylic acid and ethylenediamine with metal ions such as copper(II), cobalt(II) and nickel(II). The positive cooperativity is observed in each case; which is extended to prepare mixed metal complexes.Selective mixed metal complex formation in one pot reaction of 2,6-pyridinedicarboxylic acid and ethylenediamine with metal ions results from positive cooperativity.
Keywords: Cooperativity; Metal complexes; Self-assembly; Multi-component reactions;

Classical tetradentate chelation and novel bis(bidentate) congregation motifs of a neutral N-donor Schiff base in dinuclear cadmium(II) complexes: Synthesis, structure and luminescence behaviour by Sumitra Das; Bhola Nath Sarkar; Kishalay Bhar; Soumi Chattopadhyay; Hoong-Kun Fun; Partha Mitra; Barindra Kumar Ghosh (353-357).
Syntheses, structures and luminescence properties of three dinuclear compounds [Cd2(bpbd)3](ClO4/PF6)4 (1/2) and [Cd(bpbd)(Cl)]2(PF6)2 (3) are described in which novel bis(bidentate) congregation behaviour of tetradentate Schiff base, bpbd, is revealed along with classical tetradentate chelation motif.Three dinuclear compounds [Cd2(bpbd)3](Y)4 (Y =  ClO 4 - , 1; Y = PF 6 - , 2) and [Cd(bpbd)(Cl)]2(PF6)2 (3) [bpbd = N,N′-(bis(pyridine-2-yl)benzylidene)-1,4-butanediamine] are prepared and characterized. Structures of 1 and 3 are solved by X-ray study that reveals interesting variation in ligational motifs of bpbd from classical tetradentate chelation binding a single metal ion to bis(bidentate) congregation encapsulating two cadmium(II) centers. In the crystalline state, the dinuclear units of 1 pack through cooperative face-to-face π⋯π interactions and C–H⋯O hydrogen bonds whereas those of 3 are engaged in edge-to-face C–H⋯π interactions and C–H⋯F and C–H⋯Cl hydrogen bonds each leading to 2D sheet structure. High-energy intraligand 1(π–π∗) fluorescence at room temperature in DMF solutions and intraligand 3(π–π∗) phosphorescence in glassy solutions (DMF at 77 K) are seen in all the complexes.
Keywords: Dinuclear cadmium(II); N-donor Schiff base; Congregation; Superstructure; Luminescence;

A new sort of chemically bonded lanthanide organic–inorganic hybrid material has been constructed through the bifunctional sulfoxide molecular bridge (MSAPSi, which is functionalized 2-(methylsulfinyl) acetophenone (MSAP) by 3-(triethoxysilyl)-propyl isocyanate (TESPIC)) linking Si–O–Ti–O inorganic networks. Furthermore, the photoluminescent spectra, decay times and emission quantum efficiency of Eu3+ hybrid material are also determined.A new sort of chemically bonded lanthanide organic–inorganic hybrid material has been constructed through the bifunctional sulfoxide molecular bridge (MSAPSi, which is functionalized 2-(methylsulfinyl) acetophenone (MSAP) by 3-(triethoxysilyl)-propyl isocyanate (TESPIC)) linking Si–O–Ti–O inorganic networks. The results suggest that the obtained hybrid materials are totally amorphous without phase separation phenomenon and exhibit the characteristic luminescence of Eu3+ and Tb3+ ions. Furthermore, the decay times and emission quantum efficiency of Eu3+ hybrid material are also determined.
Keywords: Lanthanide; Organic–inorganic hybrid material; Sol–gel process; Sulfoxide linkage; Photoluminescence;

The in situ preparation of the unique complex [CoClL1][ZnI3L2] (1) (L1  = tris(1-(3,5-dimethylpyrazolyl)-methyl)amine, L2  = hexamethylenetetramine) via redox and condensation processes of zerovalent cobalt, ZnCl2 and 1-hydroxymethyl-3,5-dimethylpirazole has been reported.The in situ preparation of the unique complex [CoClL1][ZnI3L2] (1) (L1  = tris(1-(3,5-dimethylpyrazolyl)-methyl)amine, L2  = hexamethylenetetramine) via redox and condensation processes of zerovalent cobalt, ZnCl2 and 1-hydroxymethyl-3,5-dimethylpirazole has been reported. The crystal structure of 1, determined by single-crystal X-ray diffraction exhibited a distorted trigonal bipyramidal coordination sphere for [CoCl(L1)]+ ion and a distorted tetrahedral arrangement of the [ZnI3(L2)] anion, both of the C 1 point group symmetry. The structure of 1 was confirmed by IR, FTIR, UV–Vis, magnetic and thermal investigations.
Keywords: Direct synthesis; Crystal structure; Cobalt; Zinc; Urotropine; Tris(1-(3,5-dimethylpyrazolyl)-methyl)amine;

Spectroscopic studies on bis(1-amidino-O-alkylurea) copper(II) sulfate complexes where alkyl = methyl, ethyl, n-propyl or n-butyl: EPR evidence for binuclear complexes by L. Jaideva Singh; N. Shantibala Devi; S. Pramodini Devi; W. Bembee Devi; R.K. Hemakumar Singh; B. Rajeswari; R.M. Kadam (365-368).
EPR spectrum of [Cu(II)(1-amidino-O-n-butylurea)2]2(SO4)2·2H2O (4) at RT consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) of 0.0485 cm−1 and a half-field signal (ΔMs = ± 2) at ca. 1600 G, suggesting the formation of binuclear complex (S  = 1). Whereas EPR spectrum of [Cu(II)(1-amidino-O-ethylurea)2]SO4·2H2O (2) complex with zero-field splitting (ZFS) of 0.0385 cm−1 in DMSO showed a mixture of mononuclear and binuclear complex in the ratio 0.75:1.0.Four new Cu(II) Complexes viz. [Cu(II)(1-amidino-O-methylurea)2]SO4·2H2O (1), [Cu(II)(1-amidino-O-ethylurea)2](SO4)2·2H2O (2), [Cu(II)(1-amidino-O-n-propylurea)2] SO4·2H2O (3), [Cu(II)(1-amidino-O-n-butylurea)2]2(SO4)2·2H2O (4) have been synthesized and characterized. EPR spectrum of complex 4 at RT consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) of 0.0485 cm−1 and a half-field signal (ΔMs = ±2) at ca. 1600 G, revealed formation of binuclear complex (S  = 1). Whereas EPR spectrum of complex 2 in DMSO showed a mixture of mononuclear and binuclear complex in the ratio 0.75:1.0 with ZFS of 0.0385 cm−1. From the temperature dependence of the EPR signal intensity, the isotropic exchange-interaction constant J was evaluated.
Keywords: Binuclear; H-bonded copper(II) complexes; EPR; 1-Amidino-O-alkylurea; Ferromagnetic;

Unexpected activity of novel 9-oxabispidine zinc complexes in lactide polymerization by Janna Börner; Ulrich Flörke; Artjom Döring; Dirk Kuckling; Matthew D. Jones; Melanie Steiner; Matthias Breuning; Sonja Herres-Pawlis (369-371).
The zinc dichlorido and zinc diacetato complexes of the chiral tricyclic 9-oxabispidine (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.02,7] tridecane were prepared and characterized by X-ray crystallography. The latter complex was found to catalyze the solvent-free polymerization of d,l-lactide to give polylactide.The zinc dichlorido and zinc diacetato complexes of the chiral tricyclic 9-oxabispidine (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo [7.3.1.02,7] tridecane were prepared and characterized by X-ray crystallography. The latter complex was found to catalyze the solvent-free polymerization of d,l-lactide to give polylactide.
Keywords: 9-oxabispidines; Chiral diamine; Polylactide; Ring-opening polymerization; X-ray diffraction;

Two new polyoxotungstates Na3H(C3H5N2)4[{Cu(C3N2H4)2}2Cu4(H2O)2(GeW9O34)2]·27H2O (1) and Na10H10[Mn6Ge3W24O94(H2O)2]·37H2O (2) have been synthesized. Complex 1 is a Weakley-type species capped by two [Cu(C3N2H4)2]2+ units on two opposite W4O4 faces, which is the first case of the copper(II)–imidazole fragment coordinated with four bridging oxygen atoms from sandwich-type polyoxotungstogermanates. Complex 2 is a banana-shaped POM consisting of two tri-Mn substituted [Mn3GeW9O34]4− Keggin units and a hexavacant bridging cluster [GeW6O26]12−.Two new polyoxotungstates Na3H(C3H5N2)4[{Cu(C3N2H4)2}2Cu4(H2O)2(GeW9 O34)2]·27H2O (1) and Na10H8[Mn6Ge3W24O94(H2O)2]·37H2O (2) have been synthesized in aqueous solution. The polyoxoanion frameworks of the two compounds are built on the lacunary Keggin-type polyanion [GeW9O34]10−. The structure of compound 1 is a Weakley-type species capped by two [Cu(C3N2H4)2]2+ units through four bridging oxygen atoms on two opposite W4O4 faces. Compound 2 is a banana-shaped polyoxometalate consisting of two tri-Mn substituted [Mn3GeW9O34]4− Keggin units and a hexavacant bridging cluster [GeW6O26]12−. The magnetic investigations demonstrate the presence of both antiferromagnetic and ferromagnetic exchange interactions for 1 and weak antiferromagnetic interactions for 2.
Keywords: Polyoxometalate; Polyoxotungstogermanate; Sandwich; Magnetic property;

The reaction of 2,2′-ethylidenebis(4,6-di-tert-butylphenol) (EDBP-H2) with potassium gives [EDBPH·K·(THF)2] (1) in high yields. Experimental results show that potassium complex 1 is an efficient catalyst for the ring-opening polymerization of lactide in controlled fashion, yielding polymers with expectative molecular weight and low polydispersity indexes. Furthermore, the complex 1 has isotactic selectivity for the ring-opening polymerization of rac-lactide.The reaction of 2,2′-ethylidenebis(4,6-di-tert-butylphenol) (EDBP-H2) with potassium gives [EDBPH·K·(THF)2] (1) in 92% yield. Experimental results show that potassium complex 1 is an efficient catalyst for the ring-opening polymerization of lactide in controlled fashion, yielding polymers with expectative molecular weight and low polydispersity indexes. Furthermore, the complex 1 has isotactic selectivity for the ring-opening polymerization of rac-lactide.
Keywords: Potassium complex; Lactide; Ring-opening polymerization; Isotactic selectivity;

The graphical abstract represents two important aspects of our manuscript namely, SOD activity and nuclease activity. Complex 3·CH3OH, which was structurally characterized (shown in the graphical abstract), possesses E 1/2 value for MnII/MnIII couple which is in the proper range (between two arrows, −0.375 V ⩽  E 1/2  ⩽ +0.605 V vs Ag/AgCl) to exhibit SOD activity. In the redox potential value scale, values for complexes 1 and 2 are beyond the proper range and show very poor SOD activity. In terms of nuclease activity complex 3·CH3OH was more efficient as compared to complexes 1 and 2. Schiff base complexes 1 and 2 afforded lower activity for SOD as well as nuclease activity due to the lack of Nam donor in the ligand frames.Three new ligands Pyimpy (2-((2-phenyl-2-(pyridin-2-yl)hydazono)methyl)pyridine), Me-Pyimpy (1-phenyl-1-(pyridin-2-yl)-2-(1-(pyridin-2-yl)ethylidene)hydrazine) and PampH (N′-phenyl-N′-(pyridin-2-yl)picolinohydrazide) were synthesized. Hexa-coordinated mononuclear complexes [Mn(Pyimpy)2](ClO4)2 (1), [Mn(Me-Pyimpy)2](ClO4)2 (2), and [Mn(Pamp)2](ClO4)·CH3OH, (3·CH3OH) were synthesized and characterized. The molecular structure of [Mn(Pamp)2](ClO4)·CH3OH, (3·CH3OH) was determined by single crystal X-ray diffraction, which afforded distorted octahedral coordination sphere having meridionally spanning ligands. The redox properties were exploited to examine superoxide dismutase (SOD) activity using Mn(II)/Mn(III) couple. The complex 3 having ligands containing carboxamido nitrogen (Nam) donor, has been revealed to catalyze more effectively the dismutation of superoxide ( O 2 • - ) ions in xanthine–xanthine oxidase–nitro blue tetrazolium assay as compared to 1 and 2. Among the three complexes, complex 3 was found to be most effective in nuclease activity in the presence of H2O2.
Keywords: Manganese(II) and manganese(III) mononuclear complexes; Carboxamido nitrogen; DNA binding; Nuclease cleavage; Superoxide scavenging activity;

A new three-dimensional 4, 6-connected self-catenated net constructed from the [V8O23]6− polyoxoanions and metal–organic polymer by Yan-Fei Qi; Chun-Ping Lv; Yang-Guang Li; En-Bo Wang; Juan Li; Xiu-Ling Song (384-387).
A new cobalt–vanadium composite solid, Co3(btx)5(H2O)V8O23 (btx = 1,4-bis(triazol-1-ylmethyl)benzene) was obtained, exhibiting a novel three-dimensional (3D) 4, 6-connected self-catenated net constructed from novel [V8O23]6− building blocks and the {Co3(btx)5(H2O)2}6+ 3D metal–organic cation polymer.A new cobalt–vanadium composite solid, Co3(btx)5(H2O)V8O23 1 (btx = 1,4-bis(triazol-1-ylmethyl)benzene) has been synthesized. Compound 1 exhibits a novel three-dimensional (3D) 4, 6-connected self-catenated net constructed from novel [V8O23]6− building blocks and the {Co3(btx)5(H2O)2}6+ 3D metal–organic cation polymer. The magnetic study and electronic property of 1 have also been investigated.
Keywords: Polyoxovanadates; Entangled networks; Organic–inorganic hybrid; Electrochemical property; Magnetic property;

Syntheses and characterizations of two new pillared-layer coordination polymers constructed from lanthanides and mixed O-donor ligands by Xi Lin; Tianfu Liu; Jingxiang Lin; Hongxun Yang; Jian Lü; Bo Xu; Rong Cao (388-391).
Two new pillared-layer compounds (Eu2(μ3–OH)(4,4′-ABDC)1.5(C2O4) (1) and Sm2(μ3–OH)(4,4′-ABDC)1.5 (C2O4) (2)) have been obtained through self-assembly of 4,4′-azobenzene dicarboxylatic acid (4,4′-H2ABDC), oxalate, hydroxyl and LnCl3(Ln = Sm, Eu). Both compounds contain novel infinite 2D Ln layers of Lanthanide oxalates which are rarely reported.Two new pillared-layer frameworks have been obtained through self-assembly of 4,4′-azobenzene dicarboxylatic acid (4,4′-H2ABDC), oxalate, hydroxyl and LnCl3(Ln = Sm, Eu) under hydrothermal environment and characterized by TGA, IR spectroscopy, element analyses, and X-ray single crystal diffraction. The X-ray structure analyses reveal that the oxalates link the Ln(III) to form metal layers, and 4,4′-ABDC ligands work as pillars to connect adjacent layers to further extend into 3D frameworks. Their magnetic studies show that the two compounds have typical anti-ferromagnetic behaviors.
Keywords: Lanthanide; Pillared-layer; Hydrothermal; Anti-ferromagnetic;

Water-soluble NaYF4:Yb/Er upconversion nanophosphors: Synthesis, characteristics and application in bioimaging by Tianye Cao; Tianshe Yang; Yuan Gao; Yang Yang; He Hu; Fuyou Li (392-394).
This work describes the water-soluble NaYF4:Yb/Er, by replacing oleic acid with citrate to surface, can exhibit very bright luminescence in the effective detection of cancer (HeLa) cells.Water-soluble and citrate (cit) coated rare-earth upconversion nanophosphors (UCNPs) were prepared by an efficient surface ligand exchange of the oleic acid capped hydrophobic UCNPs in diethylene glycol (DEG) at high temperature. The successful surface ligand exchange of the UCNPs with citrate was confirmed by Fourier-transform infrared (FTIR) spectroscopy. Further characterizations such as TEM and XRD showed that the ligand exchange reaction had no obvious influence on chemical properties of UCNPs, such as morphology and crystallization. Furthermore, bright UC luminescence was observed when UCNPs-labeled cells were excited with 980nm near-infrared (NIR) light proving that Cit-UCNPs can be used as non-specific labels for imaging HeLa cells. These results indicate that the Cit-UCNPs are a promising candidate for use as bioimaging probes.
Keywords: Upconversion; Rare-earth nanomaterials; Surface; Luminescence;

MnO2 instead of quinones as selective oxidant of tetrapyrrolic macrocycles by Bruno F.O. Nascimento; António M.d’A. Rocha Gonsalves; Marta Pineiro (395-398).
Heterogeneous oxidation under microwave irradiation of hexahydroporphyrins and tetrahydroporphyrins to generate porphyrins and chlorins.Porphyrins and chlorins were generated through dehydrogenation of the corresponding porphyrinogen and bacteriochlorin precursors using activated manganese dioxide and focused microwave irradiation. The application of this inexpensive heterogeneous oxidant under microwave heating conditions, instead of the quinones usually employed in conventional methodologies, allowed short reaction times, simple overall work-ups and good yields.
Keywords: Porphyrin; Chlorin; Bacteriochlorin; Manganese dioxide; Microwave synthesis; Oxidation;

Description of two different two-dimensional morphologies mostly built by water in an hydrated salt of a dinuclear complex Cu(II) cation and a triazolopyrimidinate anion.The crystal structure of the compound [Cu2(OH)2(H2O)2(phen)2](dmax)2·10H2O is presented, where phen = 1,10-phenanthroline and dmax  =  4,6-dimethyl-1,2,3-triazolo[4,5-d]pyrimidin-5,7-dionato. The cationic species is a dinuclear hydroxo bridged Cu(II) complex, the charge of which is balanced by the heterocyclic anionic ligand. The main focus of the work is the analysis of the H-bond network, which includes two different two-dimensional morphologies, mostly built by water molecules. The first one includes a monodimensional tape superstructure built exclusively by interstitial water, with alternating four-member and six-member water clusters, the tapes being linked by the cationic complexes via coordinated water and hydroxyl groups. The second is formed by water molecules and the triazolopyrimidine anions. Both morphologies include H-bond rings of different sizes.
Keywords: Hydrogen bond; Water clusters; Triazolopyrimidines; Water superstructures;

Sulfoalkyl modified zirconium poly (styrene-isopropenyl phosphonate)-phosphate (ZPS-IPPA) were designed and synthesized for immobilization of the chiral homogenous salen Mn(III) catalyst by axial coordination. The linkage lengths of the sulfoalkyl modified ZPS-IPPA play an important role in ee values and yields of epoxidations. The heterogeneous catalysts are relatively stable and can be recycled nine times.Sulfoalkyl modified zirconium poly (styrene-isopropenyl phosphonate)-phosphate (ZPS-IPPA), with special structures of new type of organic–inorganic hybrid material were designed and synthesized for immobilization of the chiral salen Mn(III) Jacobsen’s homogenous catalyst by axial coordination. All the heterogeneous chiral salen Mn(III) catalysts with different linkage lengths obtained exhibited great catalytic activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. The influence of the linkage lengths on the catalytic performance was investigated. What’s more, the catalysts were easily separated from the reaction systems and could be reused for several times without significant loss of catalytic activity.
Keywords: Zirconium poly (styrene-isopropenyl phosphonate)-phosphate; Sulfoalkyl modify; Chiral salen Mn(III); Heterogeneous catalyst; Asymmetric epoxidation;

The spin gap system by self-assembly of benzyl-4-ethylpyridinium and bis(maleonitriledithiolate)niclelate(III) anion by Hong-Rong Zuo; Wen-Tao Yin; Li-Bo Liang; Qian Huang; Xing Chen; Jia-Rong Zhou; Le-Min Yang; Chun-Lin Ni; Xue-Lei Hu (408-411).
A new molecular solid [BzEtPy][Ni(mnt)2](1) by self-assembly of [BzEtPy]+([BzEtPy]+  = benzyl-4-ethylpyridinium) cation and the [Ni(mnt)2] (mnt2−  = maleonitriledithiolate) anion is obtained. The Ni(III) ions of 1 form a 1D zigzag alternating chain through Ni···S and π···π interactions, and 1 exhibits a spin gap transition around 90 K.The self-assembly of [BzEtPy]+([BzEtPy]+  = benzyl-4-ethylpyridinium) cation and the [Ni(mnt)2] (mnt2−  = maleonitriledithiolate) anion results in the forming of a new molecular solid [BzEtPy][Ni(mnt)2](1), in which the anions and cations stack into columns and the Ni(III) ions form a 1D zigzag alternating chain through Ni···S and π···π interactions between [Ni(mnt)2] anions with the Ni···Ni distances of 3.886 Å and 4.781 Å, and the four columns of cations create cubic-like large channel in which the [Ni(mnt)2] columns are located. Magnetic susceptibility measurements show that 1 exhibits a spin gap transition around 90 K.
Keywords: Maleonitriledithiolate; Benzyl-4-ethylpyridinium; Nickel(III) complex; Crystal structure; Spin gap transition;

The hydrothermal reactions of MoO3, Cu(CH3CO2)2·H2O and 5(4′-pyridyl)tetrazole yield a low temperature Cu(II)-containing material [{Cu3(4-pt)2(4-Hpt)2(H2O)2}{β-Mo8O26}]·2H2O (1·2H2O) and a high temperature Cu(I) phase, [{Cu10(4-pt)6(4-Hpt)2}{β-Mo8O26}]·2H2O (2·2H2O). A view of the structure of 2 is shown in the accompanying graphic.The hydrothermal reactions of MoO3, Cu(CH3CO2)2·H2O and 5(4′-pyridyl)tetrazole (4-Hpt) yielded a low temperature Cu(II) phase [{Cu3(4-pt)2(4-Hpt)2(H2O)2}{Mo8O26}]·2H2O (1·2H2O) and a high temperature Cu(I) material [{Cu10(4-pt)6(4-Hpt)2}{Mo8O26}]·2H2O (2·2H2O). The two-dimensional structure of 1 is constructed from β-octamolybdate clusters embedded in a { Cu 3 ( 4 -pt ) 2 ( 4 -Hpt ) 2 ( H 2 O ) 2 } n 4 n + network. The copper(II)-pyridyltetrazolate layer consists of trinuclear clusters of corner-sharing copper ‘4 + 2’ octahedra linked through the dipodal 4-pt ligands. In contrast, the three-dimensional structure of 2 contains the {β-Mo8O26}4− building block embedded in a three-dimensional { Cu 10 ( 4 -pt ) 6 ( 4 -Hpt ) 2 } n 4 n + framework. The copper(I)-pyridyltetrazolate substructure consists of chains of Cu tetrahedra and trigonal planes bridged by tetrazolate groups and connected through exo-catenate {CuN2O} trigonal planar units bonding to the pyridyl nitrogens of the dipodal ligand.
Keywords: Bimetallic oxide; Organic–inorganic hybrid material; Polyoxomolybdate building block; Copper-pyridyltetrazolate polymers;

3D copper coordination polymers based on N-heterocyclic ligands with different topology by Xiang He; Zhao-Xi Wang; Fei-Fei Xing; Ming-Xing Li (417-420).
Two novel three-dimensional (3D) coordination polymers [ Cu 3 II ( mtta ) 6 ] n (1) and [ Cu 2 II Cu 3 I ( trz ) 4 Br 3 ] n ·nH2O (2) (mtta = 5-methyltetrazolate, trz = 1,2,4-triazole) were synthesized and structurally characterized. Complex 1 shows a 3D porous metal–organic framework. By the topology analysis, the complicated architecture of 1 can be simplified to be the 4-connected diamond-type net. Compound 2 is a two-fold interpenetrating 3,5-connected 3D supramolecular framework with new topology.Two novel three-dimensional (3D) coordination polymers [ Cu 3 II ( mtta ) 6 ] n (1) and [ Cu 2 II Cu 3 I ( trz ) 4 Br 3 ] n ·nH2O (2) (mtta = 5-methyltetrazolate, trz = 1,2,4-triazole) were synthesized and structurally characterized. Complex 1 shows a 3D porous metal–organic framework. By the topology analysis, the complicated architecture of 1 can be simplified to be the 4-connected diamond-type net. Compound 2 is a two-fold interpenetrating 3,5-connected 3D framework with new topology.
Keywords: Copper; N-Heterocycle; Coordination polymer; Crystal structure;

A new pure Mo-oxide-based organic–inorganic hybrid framework templated by vanadium-substituted Keggin anions by Li-Mei Dai; Wan-Sheng You; Yang-Guang Li; En-Bo Wang; Li-Jun Qi; Jing Tang; Xiu-Li Bai (421-424).
A new polyoxometalate-templated pure Mo-oxide-based organic–inorganic hybrid framework with parallelogram grids has been hydrothermally synthesized and its electrocatalytic property was investigated.A new polyoxometalate-templated pure Mo-oxide-based organic–inorganic hybrid framework with parallelogram grids has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Its electrocatalytic property was investigated.
Keywords: Hydrothermal synthesis; Polyoxometalate; Organic–inorganic hybrid; Molybdenum; Electrochemistry;

A novel 2-D layered heterometallic iodoplumbate, [Pb3I10Cu4(phen)2] n (phen = 1,10-phenanthroline) constructed from [Pb3I10]4− iodoplumbate chains and [Cu2I4(phen)]2− entities has been hydrothermally synthesized and structurally characterized. The compound exhibits an intriguing semiconducting property with E g  = 2.62 eV. The thermochromic behavior of the compound has been also observed.A novel two-dimensional heterometallic iodoplumbate, [Pb3I10Cu4(phen)2] n (phen = 1,10-phenanthroline) constructed from [Pb3I10]4− iodoplumbate chains and [Cu2I4(phen)]2− entities has been hydrothermally synthesized and structurally characterized. The solid compound exhibits an intriguing semiconducting property with E g  = 2.62 eV. The thermochromic behavior of the compound has been also studied.
Keywords: Heterometallic iodoplumbate; Semiconducting property; Thermochromic behavior; Hydrothermal synthesis; Crystal structure;

One-dimensional supramolecular assembly of an Mn12 single molecule magnet by ligand interactions by Sheby M. George; Shariful I. Mamun; Jinkwon Kim (429-432).
Intermolecular π–π interactions between peripheral ligands of adjacent Mn12 molecules result in one-dimensional supramolecular assembly of Mn12 in the crystal.A new Mn12 complex was synthesized using ligand substitution reaction of Mn12–OAc with 4-(thiophen-3-yl)benzoic acid and complex’s structural and magnetic properties were analysed. [Mn12O12(O2CC6H4C4H3S)16(H2O)3]·14CH2Cl2 (1) crystallized in the P21/c space group. Intermolecular π–π interactions between phenyl and thiophene rings of two adjacent Mn12 molecules result in one-dimensional supramolecular assembly of 1 in the crystal. On the other hand, steric repulsion between the neighbouring molecules causes unusual ligand arrangement and coordination geometry of Mn(III) ion with five coordination. The ac magnetic study of 1 gives U eff  = 69.98 K and 1/τ 0  = 1.456 × 108  s−1 and dc reduced magnetization measurement gives S  = 10, g  = 1.95 and D  = −0.425 cm−1 showing that outer ligand distortion has little effect on the magnetic properties.
Keywords: Single molecular magnets; Mn12; Ligand substitution reaction; π–π stacking; Magnetism;

A rare macrocyclic hexazirconium(IV) bisaryloxyl N-heterocyclic carbene complex {(L)Zr(OSiMe3)(k2-[N^O])}6 (2) ( L = 1 , 3 - [ 3 , 5 - Bu 2 t - 2 - O - - ( C 6 H 2 ) CH 2 ] 2 ( C 3 H 2 N 2 ) , H[N^O] =  1 - [ 3 , 5 - Bu 2 t - 2 -OH- ( C 6 H 2 ) CH 2 ] ( C 3 H 3 N 2 ) ) was prepared and structurally characterized and shows higher catalytic ethylene polymerization activities in the presence of MAO.A rare macrocyclic hexazirconium(IV) complex with bisaryloxyl N-heterocyclic carbene ligand {(L)Zr(OSiMe3)(k2-[N^O])}6 (2) ( L = 1 , 3 - [ 3 , 5 - Bu 2 t - 2 - O - - ( C 6 H 2 ) CH 2 ] 2 ( C 3 H 2 N 2 ) , H[N^O]= 1 - [ 3 , 5 - Bu 2 t - 2 -OH- ( C 6 H 2 ) CH 2 ) ] ( C 3 H 3 N 2 ) ) was prepared from a mononuclear complex [(L)ZrCl2(THF)] (1). Complex 2 was structurally characterized and shows higher catalytic ethylene polymerization activities in the presence of methylaluminoxane (MAO).
Keywords: Zirconium; N-heterocyclic carbene ligands; Aryloxyl; Multinuclear complex; Ethylene polymerization;

The substitution reaction of 1-D precursor [Pb(μ 2-η 2-OOCClH3C6Fc)2(CH3OH)2] n 1 with phen results in one 1-D polymer[Pb(μ 2-OOCClH3C6Fc)2(phen)] n 1a. However, a mononuclear Pb(II) complex {[Pb(η 2-OOCClH3C6Fc)2(phen)]·(CH3OH)·(H2O)} 2 could be obtained from the traditional one-pot reaction. The structural integrity of precursor can be maintained in the resultant polymer. Their electrochemistry properties are also investigated.Through substituation reaction, one lead ferroceneyl carboxylate polymer, namely [Pb(μ 2-OOCClH3C6Fc)2(phen)] n 1a [Fc = (η 5-C5H5)Fe(η 5-C5H4)] was synthesized from precursor [Pb(μ 2-η 2-OOCClH3C6Fc)2(CH3OH)2] n 1. However, a mononuclear Pb(II) complex {[Pb(η 2-OOCClH3C6Fc)2(phen)]·(CH3OH)·(H2O)} 2 could be obtained from the traditional one-pot reaction of FcC6H3ClCOONa and Pb(OAc)2 with 1,10-phenantholine (phen). The electrochemical studies of 1, 1a, 2 and FcC6H3ClCOOH indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of FcC6H3ClCOOH.
Keywords: Lead; Crystal structure; Substitution reaction; Electrochemical property; Precursor;

A chiral helical Mn(II) MOF showing unusual utg topology based on d-saccharic acid by Yao-Kang Lv; Cai-Hong Zhan; Zhan-Guo Jiang; Yun-Long Feng (440-444).
A chiral helical MOF [Mn2(sac)2(H2O)2]·3.3H2O (H2sac =  d-saccharic acid) (1), showing unusual binodal 3-connected network with utg topology, has been synthesized and characterized. The structure contains right-handed 21 helical chains in three directions with hydrophilic channels. The electrochemical property has been studied, undergoing two one-electron redox processes.A chiral helical MOF [Mn2(sac)2(H2O)2]·3.3H2O (H2sac =  d-saccharic acid) (1) has been synthesized and characterized. MOF 1 crystallizes in orthorhombic system with space group P212121, and the structure contains right-handed 21 helical chains in three directions with hydrophilic channels. From the topological point of view, the framework of MOF 1 can be abstracted as an unusual binodal 3-connected network with utg topology. The electrochemical property has been studied, undergoing two one-electron redox processes.
Keywords: Metal-organic framework; d-saccharic acid; Topology; Chiral net; Cyclic voltammetry;

Synthesis, structure, and reactivity of yttrium complexes with chiral biaryldiamine-based N4-ligands by Guofu Zi; Li Xiang; Xue Liu; Qiuwen Wang; Haibin Song (445-448).
The chiral biaryl-based N4-ligands can effectively stabilize the rare earth metal chloride complexes, which offers important intermediates for the preparation of rare earth catalysts containing the M–C or M–X (X = heteroatom) bonds.The chiral biaryl-based N4-ligands, (R)-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-bis(pyrrol-2-ylmethyleneamino)-1,1′-binaphthyl (1H2) and (S)-2,2′-bis(pyrrol-2-ylmethyleneamino)-6,6′-dimethyl-1,1′-biphenyl (2H2), can effectively stabilize the chiral rare earth metal chloride complexes such as 1-YCl(dme) (3) and 2-YCl(dme) (4), which offers important intermediates for the preparation of chiral rare earth catalysts containing the M–C or M–X (X = heteroatom) bonds. For example, treatment of 3 with half equiv of 1Na2 in THF gives the binuclear complex 1-Y(thf)-1-Y(thf)-1 (5) in 70% yield. These complexes have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. The complex 5 is an active catalyst for the ring-opening polymerization of rac-lactide, affording isotactic-rich polylactides.
Keywords: Chiral N4-ligands; Yttrium complexes; Synthesis; Structure; Reactivity;

A novel DNA light switch [Ru(bpy)2pzip]2+ activated by cobalt(II) ion by Xue-Wen Liu; Ji-Ling Lu; Yuan-Dao Chen; Lin Li; Da-Shun Zhang (449-451).
A novel ruthenium(II) complex, [Ru(bpy)2pzip]2+ has been synthesized and characterized. In the presence of Co2+ or EDTA, [Ru(bpy)2pzip]2+ exhibited the “on–off–on” properties of molecular “light switch”.A novel ruthenium(II) complex, [Ru(bpy)2pzip]2+ has been synthesized and characterized. The DNA-binding properties of this complex have been studied by spectroscopic and viscosity measurements. The results indicated that the complex [Ru(bpy)2pzip]2+ bound to double-stranded DNA in an intercalation mode. In the presence of Co2+, the emission of DNA–[Ru(bpy)2pzip]2+ can be quenched. And when EDTA was added, the emission was recovered. The experiment results show that [Ru(bpy)2pzip]2+ exhibited the “on–off–on” properties of molecular “light switch”.
Keywords: Ruthenium(II) complex; Cobalt(II); DNA-binding; Light switch;

A novel 3D 3d–4f heterodimetallic coordination polymer was synthesized, which is formed with right-hand helical structure and unique (3,4)-connected four-nodal topology. The title compound displays relatively strong photoluminescence.One new three-dimensional 3d–4f heterometallic coordination polymer, namely, {[EuZn2(imdc)2(C2O4)0.5(H2O)4]·2H2O} n (1) (H3imdc = imidazole-4,5-dicarboxylic acid), has been successfully synthesized by the hydrothermal reactions of Eu2O3, Zn(NO3)2·6H2O, H3imdc, H2C2O4·2H2O and H2O. Single-crystal X-ray diffraction analysis reveals that complex 1 possesses 3D heterometallic framework containing 2D layer based on L–Zn2–L (L = imdc) helical chains and L–EuZn1–L chains. Complex 1 exhibits unprecedented (3,4)-connected four-nodal topology with Schläfli symbol (6·7·8) (6·7·9) (6·72·82·10) (7·82). Moreover, the photoluminescence property of 1 was investigated in the solid-state at room temperature.
Keywords: 3d–4f; Crystal structure; Unique topology; Helical chain; Photoluminescence;