Inorganic Chemistry Communications (v.55, #C)

Contents List (iii-xiii).

Alternating chains with the new J1J2J3J1⋯ sequence in a three-dimensional MnII complex by Huijun Li; Hongxin Cai; Zhouqing Xu; Yaxin Cai; Xin Li; Hongwei Hou (1-4).
A three-dimensional carboxylate-bridged MnII compound [Mn6(tci)4(H2O)3]·7H2O}n (1) (tci = tris(2-carboxyethyl) isocyanurate) have been synthesized. The structure contains unique manganese chains in which the MnII ions are alternatively bridged by carboxylate groups in different coordination modes. The first example of such alternating Mn chain shows Mn1–(COO)3–Mn2–(COO)2–Mn3–(COO)3–Mn1–(COO)3–Mn2-sequence arranged as J1J2J3J1S⋯ mode. Magnetic susceptibility measurement reveals an antiferromagnetism behavior derived from the topology of the chain. There is no suitable analytical expression for determining the exchange parameters in a 1-D Heisenberg ferrimagnet consisting of alternating interactions J1J2J3J1⋯. The best way to fit the magnetic behavior of these complexes is to proceed by using a Hamiltonian that corresponds to a 12-membered of S  = 5/2 with 4 fragments repeating the sequence J1J2J3. The fit was performed by means of the computer program MAGPACK. The fitting for the observed magnetic data gives J1 = − 2.31 cm− 1, J2 = − 1.60 cm− 1, J3 = − 3.10 cm− 1, zJ′  = − 0.03 cm− 1 and g  = 1.98, with R  = 7.2 × 10− 3.A three-dimensional carboxylate-bridged MnII compound [Mn6(tci)4(H2O)3]·7H2O}n (1) containing unique manganese chains have been synthesized. The first example of such alternating Mn chain was arranged as J1J2J3J1⋯ mode. Magnetic susceptibility measurement reveals an antiferromagnetism behavior derived from the topology of the chain.Display Omitted
Keywords: Carboxylate-bridged MnII compound; Unique manganese chains; Antiferromagnetism; Alternating interactions J1J2J3J1⋯;

A CoII coordination polymer, {[Co4(CIPA)2(μ 3-OH)2(H2O)4]·4H2O}n (1), based on a tri-carboxylate ligand (H3CIPA = 5-acetyloxybenzene − 1,3-dicarboxylic acid) has been obtained and characterized structurally. Compound 1 displays a two-dimensional (2D) framework based on [Co4] clusters. Thermogravimetric analysis suggests high thermal stability of compound 1, and magnetic properties measurement indicates that antiferromagnetic couplings exist between neighboring CoII centers.A novel One (6,3)-connected 2D CoII coordination polymer based on Co4 cluster, {[Co4(CIPA)2(μ 3-OH)2(H2O)4]·4H2O}n (1), has been obtained and characterized structurally. Thermogravimetric analysis suggests high thermal stability of compound 1, and magnetic property measurement indicates that antiferromagnetic couplings exist between neighboring CoII centers.Display Omitted
Keywords: Co cluster; Crystal structure; Magnetic property; Antiferromagnetic coupling;

A new (4,8)-connected topological MOF as potential drug delivery by Qing-Lin Li; Jia-Ping Wang; Wei-Cong Liu; Xiao-Yi Zhuang; Jian-Qiang Liu; Gui-Ling Fan; Bao-Hong Li; Wei-Na Lin; Jian-Hui Man (8-10).
A new compound of (NH2(CH3)2[Zn3(L)2·3.5DMF]) (1) (H4L = 1,1′,4′,1″,4″,1‴-quaterphenyl-3,5,3‴,5‴-tetracarboxylic acid 1,3,5-benzenetrisbenzoate) was synthesized and characterized. The coordination polymer shows an unusual 4,8-connected 3D net with (46)2(412·612·84) topology. The incorporation of the drug 5-fluorouracil (5-FU) into the desolvated 1 was around 22.5 wt.% per gram of dehydrated 1. 5-Fu is released in a highly controlled and progressive fashion with 92% of the drug released after 120 h. The result from this work provides a new avenue for MOF to be used as potential drug delivery.An unusual 4,8-connected 3D net with (46)2(412·612·84) topology has been synthesized. 5-Fu is released in a highly controlled and progressive fashion with 92% of the drug released after 120 h.Display Omitted
Keywords: Drug delivery; Topology; Structure;

Solid-state structural transformation of TlI supramolecular polymer comprised from cubane-type thallium complex of [Tl43-4-BN)4] (1) (4-HBN = 4-hydroxy benzonitrile) to AgI coordination polymer with three nuclear units of [Ag33-4-BN)24-4-BN)] (2) has been studied upon mechanochemical reaction of compound 1 with AgNO3.Solid-state structural transformation of three-dimensional TlI supramolecular polymer comprised from cubane-type thallium complexes of [Tl43-4-BN)4] (1) to AgI coordination polymer with trinuclear units of [Ag33-4-BN)24-4-BN)] (2) has been observed upon solid-state reaction of compound 1 with AgNO3.Display Omitted
Keywords: Supramolecular polymer; Structural transformation; Thallium; Silver; Nanostructure; Nano silver;

A new 3D framework 1 based on {Co6} cluster as node was successfully synthesized and fully characterized, which showed an 8-connected bcu topology with the Schläfli symbol of {424,64}. Furthermore, the thermal stability and magnetic property reveal that 1 displays high thermal stability and antiferromagnetic interaction among the CoII spin carries.A new 3D framework 1 based on {Co6} cluster as node was successfully synthesized, which showed an 8-connected bcu topology. The thermal stability and magnetic property reveal that 1 display high thermal stability and antiferromagnetic interaction among the CoII spin carries.Display Omitted
Keywords: 1H-1,2,4-triazole; Metal–organic framework; Hexanuclear cluster; Magnetic property;

A unique 3D Co(II)-MOF based on [Co63-OH)4]8 + n chains: Synthesis, crystal structure, and magnetic property by Guo-Wang Xu; Zhong-Long Wang; Guo-Xuan Wen; Sha-Sha Guo; Dong-Sheng Li; Jian Zhang (17-20).
A novel metal-organic framework, [Co63-OH)4(ndc)4(bip)2(H2O)2] n (1)[H2 ndc = 1,4-naphthalenedicarboxylic acid, bip = 1,5-bis(imidazole-1-yl)pentane], constructed from unique [Co63-OH)4]8 + n chains containing alternate [Co4(OH)2]6 + and [Co2(OH)2]2 + subunits, was reported, which has a new (3,3,8,12)-connected or 12-connented fcu/cubic network and shows weak antiferromagnetic interaction between the adjacent Co(II) ions mediated through the carboxylate and hydroxyl groups.A novel metal-organic framework, [Co63-OH)4(ndc)4(bip)2(H2O)2] n , constructed from unique [Co63-OH)4]8 + n chains containing alternate [Co4(OH)2]6 + and [Co2(OH)2]2 + subunits, was reported, which has 12-connented fcu/cubic network or a new (3,3,8,12)-connected net.Display Omitted
Keywords: Co(II) compound; Crystal structure; Co–O–Co chain; Magnetic property;

Two 1D concomitant, conformational supramolecular isomers of an Ag(I) complex with the ligand 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and BF4 as counterion of general formula {[Ag(bitmb)2](BF4)}n were isolated. The crystal structures nicely point out the ligand's flexibility, showing syn-conformation in 1a and anti in 1b, as well as different contributions of non-covalent interactions, participating in the formation of the corresponding supramolecular assemblies. Furthermore, the geometry around the silver ions is also influenced by the conformational changes.Two 1D genuine conformational supramolecular isomers of an Ag(I) complex of general formula {[Ag(bitmb)2](BF4)}n were isolated. The crystal structures nicely point out the ligand's flexibility, showing syn-conformation in one isomer and anti in the other.Display Omitted
Keywords: Genuine conformational supramolecular isomerism; Coordination polymers; Ag(I) complexes;

Beta-manganese dioxide (β-MnO2) nanorods have been fabricated on a large scale by a simple hydrothermal process in a wild condition. Several characterizations such as XRD, SEM, TEM and FESEM have been employed. The wave absorption properties of β-MnO2/PVDF nanocomposites have been investigated. The results indicated that the β-MnO2/PVDF nanocomposites exhibit enhanced wave absorption properties. The minimum reflection loss of the β-MnO2/PVDF nanocomposite reaches − 30.1 dB (> 99.9% attenuation) at 8.16 GHz with a filler loading of 40 wt.%, and the frequency bandwidth less than –10 dB is from 7.12 to 9.20 GHz. The main microwave absorbing mechanism has been also discussed.The wave absorption properties of the β-MnO2/PVDF nanocomposites have been investigated. The results indicated that the β-MnO2/PVDF nanocomposites exhibit enhanced wave absorption properties.The minimum reflection loss of the β-MnO2/PVDF nanocomposite reaches − 30.1 dB (> 99.9% attenuation) at 8.16 GHz with a filler loading of 40 wt.%, and the frequency bandwidth less than − 10 dB is from 7.12 to 9.20 GHz.Display Omitted
Keywords: β-MnO2 nanorods; PVDF; Nanocomposites; Wave absorption properties;

Photocleavage of DNA and adenine–thymine inclined binding by a novel ruthenium(II) complex with 3,4-dibromo-imidazo[4,5-f][1,10]phenanthroline ligand by Hai-tao Wang; Hai-hang Li; Mian-qi Huang; Wen-xiu Huang; Chen-sheng Ma; Ming-liang Wang; Chuan-xin He; Jian-hong Liu; Qian-ling Zhang (30-35).
A new ruthenium(II) complex [Ru(phen)2(ODBIP)]2 + (phen = 1,10-phenanthroline; ODBIP = 3,4-dibromo-imidazo[4,5-f][1,10]phenanthroline) has been synthesized. Binding of this complex to poly(dG–dC) DNA, supercoiled pBR322 plasmid DNA, calf thymus DNA (CT DNA), and poly(dA–dT) DNA was investigated by spectroscopic methods. The photocleavage on pBR322 DNA was also studied by agarose gel electrophoresis, and the cleavage mechanisms were further explored. The results indicated that [Ru(phen)2(ODBIP)]2 + preferentially bound to DNA at adenine–thymine base pairs by intercalation, and the complex exhibited higher DNA cleavage efficiency under visible light irradiation than under UV light irradiation. The singlet oxygen may be responsible for the DNA photocleavage.A new ruthenium(II) complex [Ru(phen)2(ODBIP)]2 + has been synthesized. Binding of this complex to poly(dG–dC) DNA, pBR322-DNA, CT-DNA and poly(dA-dT) DNA was studied and the complex preferentially bound to DNA at adenine–thymine base pairs by intercalation. The multi-wavelength visible-light induced more efficient photocleavage of DNA by complex than UV-light (upper-left). The competition assays performed with GoldView™ nucleic acid dye instead of ethidium bromide (EB) (lower-left) provided further evidence for the intercalative binding mode between the complex and DNA.Display Omitted
Keywords: Ruthenium(II) complex; DNA sequence-inclined selectivity; Intercalation; Photocleavage;

Novel enantiopure Cu(II) complexes of (R,R)-N 1,N 2-dimethyl-bis(naphthalen-1-ylmethyl)cyclohexane-1,2-diamine (1-NMCD) and (R,R)-N 1,N 2-dimethyl-bis(naphthalen-2-ylmethyl)cyclohexane-1,2-diamine (2-NMCD) ligands were synthesized and characterized by X-ray diffraction. X-ray diffraction analysis revealed that the molecular structures of the synthesized complexes were mononuclear with Cu(II) atoms in distorted square planar geometries. The diisopropoxide derivatives generated in situ catalyzed ring opening polymerization (ROP) of rac-lactide (rac-LA) in a controlled fashion and displayed unusually high activities (10 s or 25 s for complete conversion). Heterotactic enriched PLA (with P r up to 0.90) was obtained with initiator bearing 2-NMCD in CH2Cl2.Diisoproxide derivatives, generated in situ, of novel enantiopure dichloro Cu(II) complexes supported by naphthal derivatives of (R,R)-1,2-diaminocyclohexane were investigated in ROP of rac-LA, which display excellent activity and stereoselectivity. The resultant polymer gave preference for heterotactic enchainment and yielded PLA with Pr = 0.90.Display Omitted
Keywords: Enantiopure copper complexes; X-ray structure; Ring-opening polymerization; Single-site catalysts; Heterotactic-enriched polylactide;

Synthesis, structure and application to l-lactide polymerization of a new phenoxy-imine iron(III) complex by Alexandre Carneiro Silvino; André Luiz Chuwarten Rodrigues; Jackson Antônio Lamounier Camargo Resende (39-42).
A new iron(III) phenoxy-imine complex was prepared and characterized. The molecular structure of the complex was determined by X-ray diffraction study. The X-ray analysis shows that the central atom is surrounded by two molecules of ligand 2-[[(2-hydroxyethyl)imino]methyl]-phenol in a tridentate coordination mode. The neutral complex can initiate solvent-free ring opening polymerization (ROP) of l-lactide.Display Omitted

Synthesis and characterization of Cu(I) and Zn(II) complexes with new sulfur-bearing isoxazole- or pyrazole-based ligands by Neudo Urdaneta; Vanessa R. Landaeta; Rafael E. Rodríguez-Lugo; Carlos Díaz; Gustavo Santiso-Quinones; Jairo Quiroga; Braulio Insuasty (43-47).
The synthesis of the new ligands 6-(5-methyl-1,2-oxazol-3-yl)-2,3-dihydro-5H-[1,4] dithiino[2,3-c]pyrrole-5,7(6H)-dione (isox′) and 6-(3-methyl-1H-pyrazol-5-yl)-2,3-dihydro-5H-[1,4]dithiino[2,3-c]pyrrole-5,7(6H)-dione (pyraz′) and their coordination chemistry toward Cu(I) and Zn(II), was studied. The ligands and their complexes were characterized using a combination of either multinuclear NMR (1H and 13C{1H}), HRMS, FTIR or Uv–Vis spectroscopy. The solid state structures of ligand isox′ and complexes [Cu(pyraz′)2]OTf and [Zn(OOCCF3)2(pyraz′)2] were determined. Interestingly, isox′ presents a yellow luminescence in its free form. Additionally, the ability of isox′ to coordinate as an N–O bidentate ligand or as an N–S bridge between two copper centers, forming a coordination polymer, is studied. The solid state structure of this Cu(I)-isox′ 1D coordination polymer is also reported.The synthesis of the new nitrogen-based ligands isox′ and pyraz′, and their coordination chemistry toward Cu(I) and Zn(II), is described. The solid state structures of isox′, [Cu(pyraz′)2]OTf and [Zn(OOCCF3)2(pyraz′)2] were determined. Isox′ can also coordinate as an N–S bridge, forming a 1D coordination polymer, as evidenced by its solid state structure.Display Omitted
Keywords: Isoxazole-based ligand; Pyrazole-based ligand; Luminescence; Zn(II) complexes; Cu(I) complexes; 1D coordination polymer;

Cyrhetrenyl and ferrocenyl 1,3,4-thiadiazole derivatives: Synthesis, characterization, crystal structures and in vitro antitubercular activity by Cristóbal Quintana; A. Hugo Klahn; Vania Artigas; Mauricio Fuentealba; Christophe Biot; Iman Halloum; Laurent Kremer; Rodrigo Arancibia (48-50).
A new series of cyrhetrenyl and ferrocenyl 1,3,4-thiadiazoles (TDZs) were designed, synthesized and characterized. The condensation–cyclization reaction of organometallic-cyanide with the corresponding thiosemicarbazide produces the ferrocenyl-TDZs (3a–c) and cyrhetrenyl analogues (4ac). The structures of all products were inferred from their elemental analysis, 1H and 13C NMR spectra and MS. The molecular structures of 3b and 4b were confirmed using X-ray crystallography. The electronic effects of cyrhetrenyl (4a–c) and ferrocenyl (3a–c) bound directly to the thiadiazole ring have been correlated with the chemical shift of the exocyclic amine proton and 13C shift of the carbon at the 5-position. The X-ray crystal structure of 3b and 4b indicates that the rhenium compound 4b possesses a more extensive conjugated π-system. The activity of the new organometallic-TDZs was evaluated in vitro against Mycobacterium tuberculosis. The incorporation of any organometallic fragment into the thiadiazole skeleton showed a comparable but lower antitubercular activity than isoniazid.A new series of organometallic 1,3,4-thiadiazoles containing the cyrhetrenyl and ferrocenyl fragments have been synthesized and characterized. Biological evaluation against the Mycobacterium tuberculosis indicates that the incorporation of any organometallic fragment into the thiadiazole skeleton showed a comparable but lower antitubercular activity than isoniazid.Display Omitted
Keywords: Cyrhetrene; Ferrocene; 1,3,4-Thiadiazole; Tuberculosis; Anti-Mycobacterium tuberculosis;

Structural characterization of a new polymeric Cu(II) complex with unexpected chlorinated pyrazole ligand by Adaris M. Lopez_Marzo; Miguel Guerrero; Teresa Calvet; Mercè Font-Bardia; Josefina Pons (51-55).
A new coordination polymer based on copper(II) and pyrazole (pzH) ligand, [CuCl2(ClpzH)2]n, has been obtained by a very easy synthesis and green reaction conditions using water as solvent. The compound was characterized by single crystal X-ray diffraction elemental analyses, infrared and UV–Vis spectroscopies. For the first time the C(2)-chlorination of the pyrazolyl ring keeping the protonation of the N(2)–H is reported. The polymeric crystal structure consists of a one dimensional infinite neutral chain in which the copper(II) atoms are six-coordinated in a slightly distorted octahedral geometry with two nitrogen and four chlorine atoms. In this structure, intermolecular interactions have been identified and studied. Extended structure analyses revealed a novel two-dimensional network supported by intermolecular N―H―Cl and C―H―Cl hydrogen bonds, in addition to the π–π stacking interactions.The synthesis of a new [CuCl2(ClpzH)2]n compound where the C-chlorination of the pyrazole ring and the formation of a polymeric structure are unexpectedly observed. This new compound has been characterized by elemental analyses, infrared and UV–vis spectroscopies, and single crystal X-ray diffraction. Intermolecular interactions have been studied. Extended structure analyses revealed a novel three-dimensional network formed by intermolecular N―H―Cl hydrogen bonds, C―H―Cl and π–π stacking interactions.Display Omitted
Keywords: Polymeric copper(II) complex; Pyrazole; Supramolecular crystal structure;

A new dinuclear ruthenium complex 1 (L1[Ru(bda)2(picoline)]2) based on Ru–bda (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid) and dipyridyl xanthene (L1  = 4,5-dipyridyl-2,7-di-tert-butyl-9,9-dimethyl xanthene) ligand was synthesized to probe the catalytic oxidation of water. An oxygen evolution experiment displays a low catalytic water oxidation activity with a first-order reaction kinetic mechanism. The result indicates that the O―O bond formation of the dinuclear catalyst 1 follows a water nucleophilic attack pathway rather than a radical coupling pathway. The most plausible interpretation is that the steric hindrance effects of the L1 and bda ligands lead to a disadvantage in forming the face-to-face configuration of the two active sites in a one dimer molecule.A new dinuclear ruthenium complex 1 was synthesized to probe the catalytic oxidation of water. An oxygen evolution experiment displays a low catalytic water oxidation activity with a first-order reaction kinetic mechanism. The result indicates that the O―O bond formation of the dinuclear catalyst 1 follows a water nucleophilic attack pathway rather than a radical coupling pathway.Display Omitted
Keywords: Ruthenium dimer catalyst; Water oxidation; Mechanism; Kinetic study;

In this study, the new [3,5-bis(2-morpholin-4-ylethoxy)phenyl]methanol 3 has been synthesized. Then novel axially di-substituted silicon phthalocyanine 3, axially mono-substituted subphthalocyanine 5 and their quaternized derivatives 4a and 5a have been synthesized using a convenient route starting with the [3,5-bis(2-morpholin-4-ylethoxy)phenyl]methanol. The complexes are obtained in high yield and are soluble in many organic solvents. The aggregation behavior of axially di-substituted silicon phthalocyanine 3, axially mono-substituted subphthalocyanine 5 and their quaternized derivatives 4a and 5a was examined in different solvents. The effect of solvents on absorption spectra was studied in various solvents. In all studied solvents, these complexes were non-aggregated. The electrochemical properties of axially di-substituted silicon phthalocyanine 3 and axially mono-substituted subphthalocyanine 5 were also investigated by cyclic voltammetry and square wave voltammetry techniques. Cyclic voltammetry revealed two reduction couples and one oxidation couple for 4 and 5.Synthesis of axially substituted silicon phthalocyanine and subphthalocyanine. Investigation of electrochemical properties of silicon phthalocyanine and subphthalocyanine.Display Omitted
Keywords: Phthalocyanine; Silicon; Axial; Synthesis; Electrochemistry; Aggregation;

Double-layer structure, sorption and magnetism properties of metal–organic frameworks with trigonal planar ligand by Xiuling Zhang; Yongzheng Zhang; Hui Hu; Zhaohua Chen; Zaiwu Yuan (65-68).
A new double-layer metal–organic framework [Co3(tcpt)2(H2O)2] (1) has been synthesized using trigonal planar ligand 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3tcpt) as a bridging ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR, PXRD and TGA. Structure analysis reveals that compound 1 has a double-layer structure. Gas sorption measurements indicate that compound 1 exhibits selective adsorption capabilities for CO2 over CH4 and N2. Furthermore, the magnetic studies of compound 1 show antiferromagnetic interactions between Co(II) ions.A new double-layer metal–organic framework [Co3(tcpt)2(H2O)2] (1) has been synthesized using trigonal planar ligand 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3tcpt) as a bridging ligand and characterized by single-crystal X-ray diffraction. Structure analysis reveals that compound 1 has a double-layer structure. Based on the CO2 adsorption isotherm at 195 K and 1 atm, the Brunauer–Emmett–Teller (BET) surface area of guest-free framework was estimated to be 380.4 m2  g− 1. Gas sorption measurement indicates that compound 1 exhibits selective adsorption capabilities for CO2 over CH4 and N2. Furthermore, the magnetic studies of compound 1 show antiferromagnetic interactions between Co(II) ions.Display Omitted
Keywords: Trigonal planar ligand; Metal–organic framework; Gas adsorption; Magnetic studies;

Ruthenium polypyridyl complexes of general formula [Ru(bpy)3 − x(Mebpy-CN)x]2 + (x = 1,2 and 3, bpy = 2,2′-bipyridine, Mebpy-CN = 4-methyl-2,2′-bipyridine-4′-carbonitrile) can be used as visible dyes in novel solar cells formed with a porous TiO2 film (1 cm2), Pt counter-electrode and iodine/iodide as the redox mediator electrolyte dissolved in a polymeric matrix. These complexes can be anchored over the surface of nanocrystalline TiO2 through nitrile groups, as evidenced by Raman spectra of the adsorbed species. Irradiated by a solar simulator (67 mW cm− 2), the cells assembled with the Ru complexes with x = 2 and 3 as TiO2 sensitizers exhibit almost identical current–potential curves, with short-circuit photocurrents of 1.25 mA cm− 2, fill factors of 0.5 and overall efficiencies around 0.44%. The Ru complex with x = 1 and a similar Re complex did not perform as well as sensitizers. These data were consistent with results obtained from quantum efficiency curves and impedance spectra. We conclude that complexes with nitrile groups as anchoring entities are promising candidates for designing efficient DSCCs.Ruthenium polypyridines with nitrile groups as anchoring entities can sensitize TiO2 in solar cells with a Pt counter-electrode and a polymer electrolyte.Display Omitted
Keywords: Solar cells; Ruthenium polypyridines; Nitriles;

Five new compounds with mixed-ligand formulated as (H4bptc)(phen) (1), [In(phen)2Cl2](H4bptc)(NO3)(H2O) (2), [In(Hbptc)(phen)(H2O)]2 (3), In(2,6-pydc)(phen)(H2O)Cl (4), and {[In(2,6-pydc)(Ox)0.5(H2O)2](H2O)}2 (5) have been synthesized under hydrothermal conditions. Compounds 15 display white, green and blue fluorescence at 298 K in the solid state, respectively. It is shown that 1 assumes solvent-dependent photoluminescence. By contrast, the different polarities of solvents do not alter the luminescence position of 3 and 5. The thermogravimetric curves show that binuclear compounds 3 and 5 have excellent thermal stability, whose structures are stable up to 190 and 272 °C, respectively.Five new compounds with mixed-ligand formulated as (H4bptc)(phen) (1), [In(phen)2Cl2](H4bptc)(NO3)(H2O) (2), [In(Hbptc)(phen)(H2O)]2 (3), In(2,6-pydc)(phen)(H2O)Cl (4), and {[In(2,6-pydc)(Ox)0.5(H2O)2](H2O)}2 (5) have been synthesized under hydrothermal conditions. The strong hydrogen bonding and π–π interactions play an important role in governing the crystal packing and determining the formation of 2D–3D supermolecular structures. Compounds 15 display white, green and blue fluorescent at 298 K in the solid state, respectively. Binuclear compounds 3 and 5 have excellent thermal stability, whose frameworks are stable up to 190 and 272 °C, respectively.Display Omitted
Keywords: Hydrothermal condition; Fluorescence; Solvent-dependent photoluminescence; Thermal stability;

Cubane-like (COO)2(H2O)6 anion water clusters: New building blocks of two trinodal supramolecular networks with mixed-connectivity by Shengjun Deng; Jie Chen; Jingyuan Nie; Shan Liu; Xiongpeng Duan; Weiming Xiao; Ning Zhang (77-82).
Two unique discrete cubane-like (COO)2(H2O)6 anion water clusters in the two solid phase have been observed for the fist time. The two water clusters are remarkably similar and both serve as the building blocks to construct two new 3D hydrogen-bonded architectures. {[Cd(PZA)2(H2O)4]·2H2O}n (1) features a rare (3,4,6)-connected trinodal network with 3,4,6T6 topology, and {[Mn(OPZA)2(H2O)4]·2H2O}n (2) displays a (4,5,6)-connected trinodal network bearing new topology. Moreover, compound 2 exhibits an interesting reversible crystal-to-amorphous transformation upon dehydration and rehydration, while 1 only exhibits crystal-to-crystal transformation during the dehydration.Two unique discrete cubane-like (COO)2(H2O)6 anion water clusters have been observed for the fist time, and they are remarkably similar and both serve as the building blocks to construct two new 3D hydrogen-bonded architectures. And 2 exhibits an interesting reversible crystal-to-amorphous transformation.Display Omitted
Keywords: Water cluster; Trinodal; Hydrogen-bonded network; Building block; Transformation;

Seven supramolecular framework, [M(bipy)2(H2O)4][M(TC–TTF)(H2O)2] (M = Mn 1, Co 2, Fe 3, Cu 4, Zn 5 and Cd 6; H4TC–TTF = tetrathiafulvalene tetracarboxylate; bipy = 4,4′-bipyridine) and [Fe42-Cl)6(OH2)12][H2.5(TC–TTF)]4·4H2O 7 have been prepared by using a diffusion method. 16 are isomorphous and crystallize in monoclinic crystal system, space group P21/c (15), and C2/m (6), respectively. {[M(TC–TTF)(H2O)2]2 −}n is a 1D polymer anionic chain consisting of MII bridged by TC–TTF4 −. {[M(bipy)2(H2O)4]2 +}n cation forms 1D cationic chain by π···π stacks, and then are linked through O–H···O (N) hydrogen-bonding and π···π interactions to construct a 2D supramolecular net. Furthermore, the 2D nets are connected through O–H···O hydrogen-bonding interactions and form a 3D supramolecular framework. 7 displays a 3D supramolecular framework by O–H···O hydrogen-bonding and S···S interactions with a 1D open channel. Variable–temperature magnetic susceptibility measurements for 1 and 2 show antiferromagnetic coupling interactions at 1.8–300 K.Display Omitted
Keywords: Chemical synthesis; Crystal structure; Microporous materials; Magnetic properties;

Two new homometallic coordination polymers based on a carboxylate-functionalized salen ligand by Li-na Hao; Ying Lu; Zhen-Zhen He; Zhu-jun Liu; Enbo Wang (88-91).
Two new homometallic coordination polymers 1 and 2 have been prepared by the directly one-step hydrothermal reactions of a carboxylate-functionalized salen ligand with Zn(II) and Co(II) ions, respectively. 1 exhibits a 3D open framework built by [Zn44-O)(carboxylate)8] units and double Zn-salen ligands, while 2 shows a 1D chain structure constructed by cobalt ions and the ligand derived from the hydrolysis to one C=N bond of salen ligand. The preliminary fluorescence measurements of 12 show the influence of structure on the property.Two new homometallic coordination polymers 1 and 2 have been prepared by the directly one-step hydrothermal reactions of a carboxylate-functionalized salen ligand with Zn(II) and Co(II) ions, respectively. 1 exhibits a 3D open framework, while 2 shows a 1D chain structure derived from the hydrolysis of salen ligand.Display Omitted
Keywords: Salen-based; Coordination polymer; One-step synthesis; Structure; Fluorescent property;

Syntheses and characterizations of two curcumin-based cocrystals by Hongmin Su; Hongming He; Yuyang Tian; Nian Zhao; Fuxing Sun; Xiaoming Zhang; Qing Jiang; Guangshan Zhu (92-95).
Two pharmaceutical cocrystals, named Jilin University China–Cocrystal-14 (JUC-C14) and Jilin University China–Cocrystal-15 (JUC-C15), which were composed of curcumin and 4, 4′-bipyridine-N, N′-dioxide, were successfully prepared by crystal engineering strategy. The crystal structures of the two cocrystals were solved and refined by single crystal X-ray diffraction. It is indicated that the crystal structures are assembled via intermolecular interactions including hydrogen bonds and π⋯π stacking. Additionally, in the structure of JUC-C15 curcumin existed in a di-keto form which is rare in other reported curcumin polymorphs. Power X-ray diffraction, Fourier-transform infrared spectra, thermogravimetric analyses and differential scanning calorimetry were executed as well to confirm the formation of the cocrystals.Two pharmaceutical cocrystals, JUC-C14 and JUC-C15, which were composed of curcumin and 4, 4′-bipyridine-N, N′-dioxide, were successfully prepared under the similarly synthetic conditions. It is indicated that JUC-C14 exhibits 1D chain structure, while JUC-C15 is a 2D net structure linked via hydrogen bonds and π⋯π packing interactions. Additionally, in the structure of JUC-C15 curcumin existed in a di-keto form which is rare in other reported curcumin polymorphs.Display Omitted
Keywords: Curcumin; Pharmaceutical cocrystal; Single crystal X-ray diffraction; Powder X-ray diffraction; Differential scanning calorimetry;

A 3D pillared Cu-based metal–organic framework: Synthesis, structure, adsorption and catalytic properties by Man-sheng Chen; Dong-cheng Liu; Yi-fang Deng; Wei-wei Fu; Hua-hong Zou; Zi-lu Chen; Chun-mei Xia; Fu-pei Liang (96-98).
The solvothermal reaction of CuCl2·2H2O, 5-(isonicotinamido)isophthalic acid (H2INAIP) results in the formation of a porous coordination polymer [Cu(INAIP)]·DMA·H2O (1) in N,N′-dimethylacetamide. X-ray single-crystal structure analysis reveals that it is a three-dimensional non-interpenetrated pillar–layer framework with a (3,6)-connected rutile (rtl) topology. Moreover, complex 1 displays selective adsorption behavior of CO2 over N2 and catalytic property for Knoevenagel condensation.A novel 3D pillared-layer Cu(II) coordination polymer, [Cu(INAIP)]·DMA·H2O (1), has been solvothermally synthesized and characterized. Complex 1 shows a rare rtl topology net, which has selective adsorptions of CO2 toward N2 and catalytic property for Knoevenagel condensation.Display Omitted
Keywords: Copper polymer; Crystal structure; Pillar-layer; Carboxamide ligand;

Two chiral coordination polymers constructed from (1R,2R)-1,2-diaminocyclohexane derivative: Syntheses, structures and properties by Zhenzhen Xue; Hao Zhang; Tianlu Sheng; Yuehong Wen; Yong Wang; Shengmin Hu; Haoran Li; Chao Zhuo; Xintao Wu (99-102).
Two chiral coordination polymers were synthesized by using a chiral ligand (1R,2R)-1,2-bis(4-(1,2,4-triazolyl))cyclohexane to assemble with Zn(II)/Ag(I) salts. The different coordination modes of the ligand result in two diverse structures, such as a 0D structure for 1 and a 1D chain for 2, respectively. The chiral nature of compounds 1 and 2 was confirmed by circular dichroism spectra (CD) and second harmonic generation (SHG) efficiency measurements. Furthermore, the photoluminescent properties of compounds 1 and 2 have been investigated in the solid state at ambient temperature.Two Zn(II)/Ag(I) chiral coordination polymers based on (1R,2R)-1,2-diaminocyclohexane derivative have been constructed, in which different coordination modes of the ligand result in distinct structures.Display Omitted
Keywords: Chiral coordination polymers; Coordination modes; Second harmonic generation; Photoluminescence;

Two new lanthanide metal–organic frameworks (Ln-MOFs) based on Dy(III) binuclear nodes, with formulas {[NH2(CH3)2][Dy2(FDA)3(NO3)]·CH2Cl2·H2O}n (1) and [Dy2(FDA)2(ox)(glycol)2]n (2) (H2FDA = furan-2,5-dicarboxylic acid), are synthesized and structurally characterized. The building blocks of two MOFs are both binuclear clusters stabilized by carboxylic groups, but the architectures are different. MOF 1 is a rare 3,9-connected FEZNUU net with point symbol of (4.62)(410.617.89)(43), whereas MOF 2 exhibits a new topology, in which a four nodes 4,4,5,5-connected net with the point symbols of (43.52.6)(43.53.62.72), respectively. Moreover, luminescence investigation of 1 and 2 shows intense and characteristic emission bands of Dy(III) ions in the solid state.Two novel Ln-MOFs {[NH2(CH3)2][Dy2(FDA)3(NO3)]·CH2Cl2·H2O}n (1) and [Dy2(FDA)2(ox)(glycol)2]n (2) based on Dy(III) binuclear nodes were synthesized and structurally characterized. 1 is a rare 3,9-connected FEZNUU net, whereas 2 exhibits a new topology. Moreover, the luminescence properties of compounds were investigated.Display Omitted
Keywords: Dysprosium; Furan-2,5-dicarboxylic acid; Structural diversity; Topology; Luminescent properties;

Hydrothermal syntheses, crystal structures and photocatalytic properties of three POM-templated organic–inorganic hybrid compounds by Xue-jing Dui; Xiao-yuan Wu; Teng Teng; Lei Zhang; Hui-fen Chen; Wen-bin Yang; Can-zhong Lu (108-111).
Three new POM-templated organic–inorganic compounds, Cu2(3,5-bptp)2[H2SiW12O40]·4H2O (1), Ag2(3,5-bptp)2[HPW12O40]·4H2O (2), [Cu4(OH)3Cl(H2O)3(4-bpo)3](SiW12O40)·5H2O (3) (3,5-bptp = 3,5-bis(3-(pyrid-4-yl)-1,2,4-triazolyl)-pyridine, 4-bpo = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole) were hydrothermally synthesized and characterized by elemental analysis and single crystal X-ray diffraction. Crystal structural analysis indicates that compounds 1 and 2 are isostructural and show one dimensional zigzag chains with [H2SiW12O40]2 − as guest molecules. Compound 3 is two dimensional sheets constructed from [Cu4(OH)3Cl(H2O)3] clusters and 4-bpo ligands with [SiW12O40]4 − as guest molecules. Furthermore, the photocatalytic degradation of methyl orange (MO) with 3 was studied under visible light irradiation, indicating excellent photocatalytic activity.Display Omitted
Keywords: Polyoxometalate-templated; Organic–inorganic compounds; Photocatalytic;

A helical salicyladoxime-based manganese triangle chain with single-molecule magnet behavior by Po-Yeng Feng; Chen-I Yang; Po-Jung Huang; Gene-Hsiang Lee; Hui-Lien Tsai (112-115).
The reaction of 2-hydroxyphenylpropanone oxime (Et-H2salox) with Mn(NO3)2·4H2O, NEt3 and 1,3-bis(4-pyridyl)propane-N,N′-dioxide (bppo) in EtOH/H2O mixture afforded a one-dimensional coordination polymer with the formula [Mn3O(Et-salox)3(bppo)(MeOH)(H2O)3](NO3)0.5(Et-Hsalox)0.5·MeOH·H2O (1·MeOH·H2O). 1·MeOH·H2O had a manganese triangle structure, [MnIII 3O]7 +, which was used as a building unit for a subsequent assembly of an oximate and central oxide. The flexible bppo ligand linked the units, resulting in the formation of a 1D helical structure. Variable temperature direct current magnetic susceptibility measurements of complex 1·MeOH·H2O were carried out. Exchange interactions of the metal centers of complex 1·MeOH·H2O were examined, and the results indicate that both ferro- and antiferromagnetic interactions simultaneously coexist in 1·MeOH·H2O, resulting in an S  = 2 ground state. Moreover, complex 1·MeOH·H2O shows the frequency dependence of the out-of-phase component in alternating current magnetic susceptibility measurements, indicating single-molecule magnet behavior with U eff  = 28 K and τ 0  = 1.8 × 10− 9  s.A one-dimensional complex 1·MeOH·H2O showed the slow magnetic relaxation of a single-molecule magnet behavior with the U eff  = 28 K and τ 0  = 1.8 × 10− 9  s.Display Omitted
Keywords: Helical chain; Magnetic anisotropy; Single-molecule magnet; Manganese complex; Oximate ligand;

Structural transition between a (4,4)-net and a CdI2-net in Cd(II) compounds and conversion from a mixture to a pure substance by Sheng-Run Zheng; Shao-Yun Yin; Mei Pan; Ling Chen; Bin-Bin Du; Ya-Jun Hou; Kai Wu; Yi-Xuan Zhu; Ji-Jun Jiang (116-119).
The coordination of a rigid triangular ligand 2,4,6-tris[4-(1H-imidazole-1-yl)phenyl]-1,3,5-triazine (TIPT) with Cd(II) ions afforded two compounds with structural motifs of a CdI2-type and a (4,4) network for anions OTf (CF3SO3 ) and OTs (p-CH3C6H5SO3 ), respectively, between which structural transition can be induced by anion exchange via solvent-mediated recrystallization process. Using this method, a pure substance can be obtained from a mixture under the excess of certain kind of anions.Structural transition between (4,4)-net and CdI2-net can be induced by anion exchange via solvent-mediated recrystallization process in Cd(II) complexes.Display Omitted
Keywords: Structural transition; Network; Anion exchange; Solvent-mediated;

Self-assembly and magnetic behavior of 2-aldehyde-8-hydroxyquinolinate-based lanthanide complex by Fangzheng Duan; Lingzhi Liu; Chunyu Qiao; Huimin Yang (120-122).
Self-assembly reaction of Ln(NO3)3.6H2O, 2-aldehyde-8-hydroxyquinoline and histamine dihydrochloride affords two mononuclear complex [Ln(hma)(NO3)2(CH3OH)]∙0.5C4H10 (Ln = Tb (1), Dy (2); Hhma = N-(2-(8-hydroxylquinolinyl)methane(2-(4-imidazolyl)ethylamine)). The structural analysis indicates that they are isomorphous where the Ln3 + is ligated to one ligand, two nitrates and one methanol molecule. Variable temperature magnetic susceptibility studies reveal the presence of antiferromagnetic interactions in 2 and the dynamic measurement reveals that 2 displays single molecular magnet behavior below 10 K under an applied field of 2000 Oe.The mononuclear dysprosium complex, constituted of multidentate ligand, nitrates and methanol molecule, exhibits slow relaxation of the magnetization.Display Omitted
Keywords: SMM; Lanthanide; Magnetic; 2-Aldehyde-8-hydroxyquinoline;

Three porous and robust metalloporphyrin frameworks exhibiting preferable gas storage by Li Zhang; Chen Wang; Xin Zhao; Fan Yu; Feng-Feng Yao; Jun Li (123-128).
We have achieved success in obtaining three novel two-dimensional porous metalloporphyrin frameworks (MPFs) through solvothermal reactions, by using 5,15-di(4-pyridyl)-10,20-bis(3,4,5-trifluorophenyl) porphyrin (trans-Py2(F3-ph)2Por) metalated with Fe (1), Co (2), and Ni (3) salts respectively. TGA reveals that they all have high thermal stabilities. Gas adsorption studies indicate that three MPFs have relatively preferable H2 uptake capacities and the selective adsorption of CO2 over N2.Three novel two-dimensional Fe(III), Co(II), and Ni(II) metalloporphyrin frameworks (MPFs) have been successfully synthesized and characterized, three complexes not only exhibit high thermal stabilities and porosity, but also have relatively preferable H2 uptake capacities and the selective adsorption of CO2 over N2.Display Omitted
Keywords: Metal–organic frameworks; Metalloporphyrin frameworks; Crystal structure; Porous material; Adsorption;

Artificial metallopeptidases: Protein cleavage by molybdenum(VI) peroxo α-amino acid complexes by Benchawan Jityuti; Apinya Buranaprapuk; Teerayuth Liwporncharoenvong (129-131).
Three molybdenum(VI) peroxo α-amino acid complexes, MoO(O2)2(α-aa) (H2O) (aa = leucine, glutamine and glycine), were prepared and used as artificial proteases for site-specific cleavage of porcine pepsin. The reaction was activated by incubation of the MoO(O2)2(α-aa) (H2O)–protein mixture at 37 °C (2–24 h). All three molybdenum complexes resulted in different cleavage sites, indicating different binding sites on the protein. Charges and the lengths of the amino acid side chains may distribute in the variation of the probe binding sites. The study can provide a new approach for the footprinting of metal binding sites on proteins in the future.Display Omitted
Keywords: Cleavage reactions; Pepsin; Molybdenum complexes; Protein–metal interactions;

Coupling of cyclohexene oxide (CHO) and carbon disulfide (CS2) catalyzed by the asymmetric bis-Schiff-base Zn(II) complex by Yaoju Liu; Xingmei Zhang; Zhao Zhang; Lin Liu; Daidi Fan; Xingqiang Lü (132-134).
Based on the self-assembly of the asymmetric bis-Schiff-base ligand H2L (H2L  = 4-((E)-(2-((E)-3,5-dibromo-2-hydroxybenzylideneamino)phenylimino)(phenyl)methyl-1-(4-chlorophenyl)-3-methyl-1H-pyrazol-5-ol) and Zn(OAc)2·2H2O, a new [Zn(L)] (1) was obtained and shown to efficiently catalyze the coupling of CHO (cyclohexene oxide) and CS2 (carbon disulfide) in activation with [PPN]Cl (PPN+  = bis(triphenylphosphoranyidene)-ammonium), n-Bu4NBr or n-Bu4NI, where both poly[thio]carbonates and cyclic [thio]carbonates were produced, and the strong O/S exchange afforded the limited formation of trithiocarbonate in the cyclic [thio]carbonate byproducts.An asymmetric bis-Schiff-base Zn(II) complex 1 was shown to efficiently catalyze the coupling of CHO and CS2 in activation with one of three co-catalysts of [PPN]Cl, n-Bu4NBr and n-Bu4NI to afford the formation of both poly[thio]carbonate and cyclic [thio]carbonates, where the optimal procedure was observed at 80 °C and a 1:1 CHO to CS2 loading molar ratio to afford poly[thio]carbonate with a Mn of 16883 g/mol and trithiocarbonate as the main cyclic [thio]carbonate byproduct due to the strong O/S exchange.Display Omitted
Keywords: Asymmetric bis-Schiff-base Zn(II) complex; Coupling of CHO and CS2; Poly[thio]carbonate and cyclic [thio]carbonates; O/S exchange;

Green oxidation of alcohols in water by a polyoxometalate nano capsule as catalyst by Elham Nikbakht; Bahram Yadollahi; Mostafa Riahi Farsani (135-138).
In this work a water soluble polyoxometalate nano capsule, HxPMo12O40  ⊂ H4Mo72Fe30(CH3COO)15O254, with high stability was evaluated for the oxidation of various alcohols into the corresponding aldehydes and ketones by hydrogen peroxide. This environmentally and economically valuable catalyst allowed for using water as solvent and has not required any organic solvents. In the presence of very low amounts of catalyst high to excellent yields and selectivity were obtained.In this work green and valuable oxidation of various alcohols to aldehydes and ketones by a water soluble POM nano capsule has been developed. By low amounts of this catalyst high to excellent yields and selectivity were obtained.Display Omitted
Keywords: Keggin-type polyoxometalate; Keplarates; Catalysis; Oxidation; Alcohols; Hydrogen peroxide; Water;

Palladium (II) and platinum (II) complexes containing organometallic thiosemicarbazone ligands: Synthesis, characterization, X-ray structures and antitubercular evaluation by Rodrigo Arancibia; Cristobal Quintana; Christophe Biot; Manuela E. Medina; Séverine Carrère-Kremer; Laurent Kremer; A. Hugo Klahn (139-142).
A new series of palladium (II) and platinum (II) complexes containing ferrocenyl and cyrhetrenyl thiosemicarbazone ligands were synthesized and characterized. The two-step reaction of the organometallic thiosemicarbazones with i) K2MCl4 and ii) PPh3 and their subsequent recrystallization from CH2Cl2/hexane yielded the binuclear complexes [Mˋ{MLn5-C5H4)C(H)=NN=C(S)NHR}–(Cl)(PPh3)] (M′=Pd, Pt; MLn =Re(CO)3, FeCp; R=H, CH3). The structures of the products were inferred from elemental analyses and IR, 1H and 31P NMR spectroscopies. The molecular structures of 2b and 3d were confirmed by single crystal X-ray analysis. All complexes were screened in vitro against Mycobacterium tuberculosis and exhibited only moderate activity in the low micromolar range.Pd(II) and Pt(II) complexes containing ferrocenyl and cyrhetrenyl thiosemicarbazone ligands were synthesized and characterized by spectroscopy and X-ray crystallography. The chelation of organometallic-TSCs through the thiolate form was inferred by 1H-NMR and confirmed by X-ray crystallography studies. The activity of the new Pd(II) and Pt(II) complexes was evaluated in vitro against Mycobacterium tuberculosis. All complexes showed only moderate antitubercular activity.Display Omitted
Keywords: Organometallic thiosemicarbazone complexes; Cyrhetrene; Ferrocene; Mycobacterium tuberculosis; Antitubercular activity;

Tuning structural topologies of two coordination polymers via alter N-donor auxiliary ligand by Hui-Hui Miao; Guo-Ping Yang; Bo Liu; Wei-Ping Wu; Lin Cui; Yao-Yu Wang (143-148).
Based on the N-donor auxiliary ligand effect, two new Ni(II) coordination polymers [Ni2(HL)2(bpe)2] (1) and [Ni(HL)(bipy)(H2O)2] (2) [H3L = 2-(4′-carboxyphenyl)terephthalic acid; bpe = 1,2-bis(4-pyridyl)ethane; bipy = 4,4′-bipyridine] have been successfully synthesized and characterized by single-crystal X-ray diffraction study, elemental analysis, IR spectra, TGA and powder X-ray diffraction (PXRD). This work presents a comparative study on the tuning of structural topologies by using two N-donor ligands with different lengths as auxiliary ligands. The structural determination reveals that complex 1, incorporating bpe ligands, features a three-dimensional (3D) 4-connected 4-fold dia interpenetrating architecture with the point symbol of 66, while 2, containing bipy ligands, exhibits a two-dimensional (2D) sql layer structure with a 4-connected (44·62) topology. Moreover, the magnetic properties for 1 and 2 were also measured and compared on account of their different structures.Two new CPs based on an unsymmetrical tricarboxylic acid and bpe or bipy have been successfully synthesized and characterized under the identical conditions. The results indicated that the flexibility and length of the N-donor auxiliary ligands play the significant roles in adjusting the coordination architecture and characters of the CPs.Display Omitted
Keywords: Coordination polymer; Ni(II) complex; N-donor ligands; Topology; Magnetic properties;

The composite material based on Dawson-type polyoxometalate and activated carbon as the supercapacitor electrode by Anqi Mu; Jiansheng Li; Weilin Chen; Xiaojing Sang; ZhongMin Su; Enbo Wang (149-152).
A supercapacitor electrode assembled from activated carbon (AC) and (NH4)6[P2Mo18O62]·14.2H2O (P2Mo18) was fabricated for the first time, and showed remarkable electrochemical performance ascribed to the synergy of the double layer capacitance of AC and the pseudocapacitance of P2Mo18. The investigations indicate that the AC/P2Mo18 electrode exhibits a specific capacitance of 275 F g− 1 at a high current density of 6 A g− 1, which is substantially larger than the 182 F g− 1 of the AC electrode. In addition, the AC/P2Mo18 electrode possesses a remarkable rate capability (89%) when the current density is increased from 2 to 6 A g− 1.An AC/P2Mo18 composite material exhibiting a higher specific capacitance (275 F g− 1) than an AC electrode (182 F g− 1) at a high current density of 6 A g− 1 and possessing a remarkable rate capability (89%) when the current density increased from 2 to 6 A g− 1 has been introduced into a supercapacitor electrode for the first time.Display Omitted
Keywords: Polyoxometalates; Supercapacitor; Composite materials; Carbon materials;

Strengthening gold–gold bonds by complexing gold clusters with noble gases by Luca M. Ghiringhelli; Sergey V. Levchenko (153-156).
We report an unexpectedly strong and complex chemical bonding of rare-gas atoms to neutral gold clusters. The bonding features are consistently reproduced at different levels of approximation within density-functional theory and beyond: from GGA, through hybrid and double-hybrid functionals, up to renormalized second-order perturbation theory. The main finding is that the adsorption of Ar, Kr, and Xe reduces electron–electron repulsion within gold dimer, causing strengthening of the Au―Au bond. Differently from the dimer, the rare-gas adsorption effects on the gold trimer's geometry and vibrational frequencies are mainly due to electron occupation of the trimer's lowest unoccupied molecular orbital. For the trimer, the theoretical results are also consistent with far-infrared multiple photon dissociation experiments.
Keywords: Electronic structure calculations; Vibrational spectroscopy; Neutral gold clusters; Covalently bonded rare-gas complexes;

One novel 3D cadmium coordination polymer, namely, {[Cd2(bptc4 −)(ox2 −)0.5(H2O)2] · 4.5H2O}n (1), has been hydrothermally synthesized through a reaction of 2,3′,4,5′-biphenyltetracarboxylic acid (H4bptc) with divalent cadmium salt in the presence of a second ligand (ox = oxalic acid). X-ray single crystal structure analysis reveals that tetranuclear cadmium clusters are formed by linking two Cd1 and two Cd2 ions with carboxyl groups. Each ox2 − ligand, with a bidentate chelating mode, connects two Cd2 ions from two adjacent tetranuclear clusters to afford 1D zigzag cadmium cluster chains. Furthermore, 1D chains are connected by bptc4 − ligands to extend a 3D framework with one-dimensional channels along the [001] direction. From a topology view, complex 1 exhibits an unprecedented 2-nodal 4, 10-connected net with the Schläfli symbol of {46}2{49. 512.622.72}. The luminescence analyses reveal that complex 1 shows an emission maximum at 437 nm, which may be attributed to the intra-ligand transition. A red shift of 31 nm compared with H4bptc ligand was observed and the luminescent decay lifetime is 2.74 ns, which indicates that it might be a potential blue light-emitting candidate. In addition, it was also characterized by elemental, IR spectra, PXRD and TG analyses.One novel 3D tetranuclear cadmium coordination polymer is synthesized and characterized. 1D zigzag cadmium cluster chains are formed through linking two adjacent tetranuclear cadmium clusters with ox2 − ligands. The whole framework exhibits an unprecedented 2-nodal 4, 10-connected net with the Schläfli symbol of {46}2{49. 512.622.72}.Display Omitted
Keywords: Coordination polymer; Metal-organic frameworks; Luminescence; 2,3′,4,5′-Biphenyltetracarboxylic acid;

Methoxyaryl substituted aluminum ketiminate complexes and its activity in ring opening polymerization processes by Roman Olejník; Jana Bažantová; Zdeňka Růžičková; Jan Merna; Zdeněk Hošťálek; Aleš Růžička (161-164).
The synthesis of dimethyl aluminum (L o AlMe2 ) and chloromethyl aluminum (L o AlMeCl) complexes containing ketiminate ligand [(2-MeO)C6H4]N(H)C(Me) = CHC(Me) = O (L o H) is reported along with the preparation of L o 3Al from L o H and LiAlH4, and ionic [L o′ Al(thf)3]I from L o AlMe2 and I2. In the later complex the pseudooctahedral geometry of the aluminum ion by terdentate ligand {[(2-O)C6H4]NC(Me) = CHC(Me) = O}2 − (L o′ ), originated from L o ligand by the methyl group abstraction, and three THF molecules are observed. Structures of these complexes were determined by X-ray techniques. The activity of L o AlMe2 and L o AlMeCl as initiators of ring opening polymerization of ε-caprolactone, trimethylene carbonate and l-lactide, and (co)polymerization of cyclohexene oxide and carbon dioxide was studied.Four aluminum(III) complexes containing bifunctional ketiminate ligand were synthesized and tested for catalytic activity in ring opening polymerization of lactone, carbonate and oxirane species.Display Omitted
Keywords: Aluminium; Ketiminate; Ring Opening Polymerization; Structure;

Two new lanthanide (III) coordination polymers, namely, {[Eu3(μ 3-HPyIDC)4]·Cl}n, (1) and {[Tb2(μ 3-HPyIDC)2(μ 2-Ox) (H2O)2]·4H2O}n (2) (H3PyIDC = 2-(3-Pyridyl)-1H-4, 5-imidazoledicarboxylic acid; Ox = oxalate), were successfully synthesized under hydro(solvo)thermal conditions and structurally characterized. Compound 1 displays a 3D framework with new (3,4)-connected {4.8.10}4{4.84.12}2{42.84} topology built by 3-connected μ 3-HPyIDC nodes and 4-connected metal ions. Compound 2 exhibits a rare (3,4)-connected dmc topology, in which μ 3-HPyIDC anions are 3-connected nodes and metal ions are 4-connected nodes. Moreover, the thermal stabilities and luminescence of compounds 12 were also investigated.Two novel three-dimensional Ln(III) coordination frameworks with (3,4)-connected topologies based on H3PyIDC with/without ox auxiliary ligands were successfully obtained.Display Omitted
Keywords: Lanthanide coordination polymers; 2-(Pyridine-3-yl)-1H-4,5-imidazoledicarboxylic; Topology; Photoluminescence;