Inorganic Chemistry Communications (v.67, #C)

Contents List (iii-x).

Titanium complexes based on pyridine containing dialcohols: Effect of a ligand by Ekaterina A. Kuchuk; Badma N. Mankaev; Kirill V. Zaitsev; Yuri F. Oprunenko; Andrei V. Churakov; Galina S. Zaitseva; Sergey S. Karlov (1-5).
Substituted 2,6-bis(hydroxyalkyl)pyridines, H2L, 13 (2,6-Py(CH2(X)OH)(CH2(Y)OH), X = Y =  cyclo-C6H10, 1; X = Y = 1-Ad, 2; X = CPh2, Y = CH2CPh2, 3), were used as ligands for the synthesis of titanium(IV) complexes, (i-PrO)2Ti(L), 1a3a. On the contrary, application of related dialcohol based on 2,2′-bipyridine, H2L′, 5 (2,2′-bipy-6,6′-(CH2Ph2OH)2), resulted in titanyl complex, (L′)Ti=O, 6. The molecular structure of 6 was investigated by X-ray analysis. Compounds 1a and 3a were tested as initiators in ring-opening polymerization of l-lactide and ε-caprolactone showing moderate activity.The structure of the ligand determines the nature of the titanium complex formed. Substituted 2,6-bis(hydroxyalkyl)pyridines give typical complexes. On contrary, (2,2′-bipy-6,6′-(CH2Ph2OH)2) results in complex with TiO bond.Display Omitted
Keywords: Polydentate ligand; Pyridine dialcohol; Titanium; Complex; Titanyl; Ring-opening polymerization;

We reported herein an unprecedented quaternary heterometallic framework, namely, [AgPb2I3(OH)2] (1), which was successfully produced under ionothermal condition. In the title compound, [Pb4(OH)4] cubane and [Ag2I6] building blocks are jointed together to give a (6,6)-connected pcu topology. Compound 1 shows not only remarkable luminescent emissions, but also semiconducting properties tuned by the corresponding metal halide components.A novel quaternary heterometallic framework based on [Pb4(OH)4] cubane and [Ag2I6] building blocks was successfully produced under ionothermal conditions, which shows tuneable semiconducting and luminescent properties.Display Omitted
Keywords: Quaternary heterometallic framework; [Pb4(OH)4]; [Ag2I6]; Semiconducting and luminescent properties;

A polyhedron-based cobalt-organic framework for gas adsorption and separation by Lei Zhang; Wenbin Yang; Xiao-Yuan Wu; Miao Huo; Can-Zhong Lu; Wen-Zhe Chen (10-13).
A cobalt-organic framework (1) consisted of close-packed polyhedral cages is isostructural to CPM-35-Ni. The activated sample (1a) can adsorb high H2 uptake of 88.3 cm3  g− 1 (0.79 wt.%) at 77 K and 1.0 bar. Remarkably, 1a shows high CO2 adsorption capacity and good adsorption selectivity for CO2 over CH4 and N2.Large single crystals of a 3D cobalt-organic framework composed of close-packed polyhedral cages show not only high H2 and CO2 uptakes but also good adsorption selectivity for CO2 over CH4 and N2.Display Omitted
Keywords: Polyhedron cages; MOF; H2 and CO2 uptakes; CO2/CH4 and CO2/N2 selectivity;

A 7-fold interpenetrated 3D porous coordination polymer (PCP) with nitrobenzene sensing properties by Peng Wang; Ji Xu; Qi-Dong Zhuo; Yun-Sheng Ma; Hong-Jian Cheng; Xiao-Yan Tang; Rong-Xin Yuan (14-16).
A Zn(II)-based porous coordination polymer (PCP) {[Zn2(ppt)2(fdc)(H2O)2]·2DMF}n (1) (H2fdc = 9H-fluorene-2,7-dicarboxylic acid, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) has been synthesized under hydrothermal conditions. The resulting PCP shows a 7-fold interpenetrated 3D structure that can be simplified as a diamond-like structure with Zn1 as node and fdc and Zn(ppt)2 as spacers. It exhibits strong luminescence at room temperature in solid-state. Luminescent property study shows that 1 can be used as a fluorescent sensor for nitrobenzene (NB).A Zn-based 7-fold interpenetrated 3D porous coordination polymer (PCP) was synthesized and characterized. The compound could act as a sensor for nitrobenzene.Display Omitted
Keywords: Zinc coordination polymer; 7-fold interpenetrated; Fluorescence; Nitrobenzene sensing;

Two Ag(I) coordination polymers, namely [Ag(L)(p-bdc)0.5] n (1) and [Ag(L)(p-bdc)0.5·2H2O] n (2) (L = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, p-H2bdc = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions by different silver(I) salt. Complex 1 is a 2D Borromean entanglement involving 3-fold (6,3) honeycomb networks. Nevertheless, complex 2 display a 1D ladder-like chain structure. Both complexes are ultimately extended into 3D supramolecular frameworks via Ag···O interactions and π···π interactions. The fluorescence and catalytic activities of two complexes for the degradation of methyl orange by sodium persulfate were addressed.Two Ag(I) coordination polymers, namely, [Ag(L)(p-bdc)0.5] n (1) and [Ag(L)(p-bdc)0.5·2H2O] n (2) (L = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, p-H2bdc = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions by different silver(I) salts. Complex 1 is a 2D Borromean entanglement involving 3-fold (6,3) honeycomb networks stabilized by Ag···O interactions. Nevertheless, complex 2 display a 1D ladder-like chain structure.Display Omitted
Keywords: Borromean link; Ag···O interaction; crystal structure; Ag(I); catalytic property;

Synthesis, characterization and antitumoral activity of new di-iron(III) complexes containing naphthyl groups: Effect of the isomerism on the biological activity by Samila R. Morcelli; Milton M. Kanashiro; Dalber R.S. Candela; M. Alzamora; Adolfo Horn; Christiane Fernandes (22-24).
The synthesis, physico-chemical characterization and cytotoxicity of two di-iron(III) complexes toward three human leukemia cell lines (THP-1, U937 and Molt-4) are reported: [(Cl2)FeIII(μ-HL1)2FeIII(Cl2)]·3H2O (1) and [(Cl2)FeIII(μ-HL2)2FeIII(Cl2)] (2), where HL1 and HL2 are isomers and contain pyridine, phenol, amine and alcohol moieties with a naphthyl pendant unit. These compounds were characterized by a range of physico-chemical methods. Electrochemical studies reveal the maintenance of the dinuclear arrangement in solution, which is supported by ESI(+)-MS studies. Mossbauer spectra consist of a unique doublet indicating equivalent iron centers in the whole sample. The hyperfine parameters are typical of high-spin iron(III). Complex (1) is more active than complex (2), showing an effect of the isomerism on the antitumoral activity. The comparison between these data and those obtained for complexes containing copper and cobalt reveals that the isomerism of the ligand, the nature of the metal centers, the nuclearity and the kind of cell line exert a great influence on the biological activity.
Keywords: Dinuclear iron(III) complexes; Mössbauer; ESI(+)-MS; Electrochemical studies; Antitumoral activity; Isomerism;

The new dinuclear rhodium complex [(Cp*RhCl)2(bpp)](PF6) ([1](PF6), Cp* = pentamethylcyclopentadienyl, bpp = 3,5-bis(2-pyridyl)pyrazolate) was synthesized by the reaction of [Cp*RhCl2]2 with 3,5-bis(2-pyridyl)pyrazole (bppH). [1](PF6) was characterized by 1H- and 13C{1H}-NMR spectroscopy and X-ray diffraction. The distance between the two Rh atoms in [1](PF6) is 4.746(3) Å. A cyclic voltammogram of [1](PF6) in acetonitrile shows three-step reduction peaks at E pc  = − 1.44, − 1.68 and − 1.88 V (vs. Fc+/Fc), which are assigned to the reduction of the two Rh(III) centers and the bpp ligand, respectively. [1](PF6) catalyzes the reduction reaction of NAD+ (nicotinamide adenine dinucleotide) using HCO2 as a reductant.Display Omitted
Keywords: Rhodium; Dinuclear complex; Bridging ligand; Cyclic voltammetry; Reduction catalyst;

Preparation and photocatalytic property of spindle-like MIL-88B(Fe) nanoparticles by Bo Xu; He Yang; Yong Cai; Hongxun Yang; Cuncheng Li (29-31).
Iron(III) based nanoparticles MIL-88B(Fe) with spindle-like morphology were synthesized by a facile method. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) revealed that the MIL-88B(Fe) nanoparticles had an uniform size of about 385 nm in length and 195 nm in width. The obtained nanoparticles were further characterized by powder X-ray diffraction (XRD) and ultraviolet-visible spectroscopy (UV–vis). Moreover, as MIL-88B(Fe) shows obvious adsorption in the visible region, it has good degradation activity for methylene blue (MB) and rhodamine B (RB) dye under visible light.MIL-88B(Fe) particles with spindle-like morphology were synthesized and showing good degradation activity for methylene blue and rhodamine B dye.Display Omitted
Keywords: Nanoparticles; MIL-88B(Fe); Optical materials; Photocatalysis;

The complex Fe(II)(binap)Cl2 with binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphtyl shows an intraligand phosphorescence in the solid state under ambient conditions. Surprisingly, low-energy LF (ligand field) excited states do not quench this emission. Tetrahedral Fe(II) complexes are d6 high-spin complexes with a quintet ground state and a quintet state as the only LF excited state. However, this excited quintet is so low in energy that it may not be able to interfere with the observed phosphorescence. This apparently applies to Fe(binap)Cl2 which shows its LF absorption at λmax  = 3100 nm and IL phosphorescence at λmax  = 505 nm. It is anticipated that the present report will stimulate more studies of this subject.Solid Fe(II)(binap)Cl2 shows a triplet emission from a IL (binap) excited state at r.t. It is suggested that a lower LF excited quintet state is not able to quench the IL phosphorescence because it is too low in energy.Display Omitted
Keywords: Iron(II) complexes; Binap complexes; Luminescence; Phosphorescence;

Organic-inorganic hybrid compound (HIm)6[(CdCl4)(CdCl6)] (Im = imidazole) shows a striking dielectric transition and relaxation between 120 and 180 K. Variable-temperature single crystal structure analysis and dielectric measurement reveal one half of the HIm cations in the crystal undergoes a transition between the static and dynamic disorders.Motional changes of one half of the HIm cations in the imidazolium-based crystal (HIm)6[(CdCl4)(CdCl6)] shows dielectric transition and relaxation behaviors between 120 and 180 K.Display Omitted
Keywords: Phase transition; Dielectric transition; Disorder; Imidazole; Cadmium;

A cyclometalated iridium(III) complex that inhibits the migration and invasion of MDA-MB-231 cells by Jinquan Wang; Xiaojuan Hou; Zizhuo Zhao; Huaben Bo; Qizhu Chen (40-43).
A cyclometalated iridium(III) complex, [Ir(ppy)2(PCN)]Cl (Ir1, ppy = 2-phenylpyridine, PCN = 2-(4-cyanophenyl)imidazo[4,5-f] [1,10] phenanthroline), was synthesized and characterized in the present study. Ir1 inhibited the proliferation, migration and invasion of MDA-MB-231 human breast cancer cells in a dose-dependent manner. Moreover, Ir1 down-regulated the phosphorylation of AKT/ERK signal pathways. According to confocal fluorescence microscopy analysis, Ir1 was primarily localized within the mitochondria and induced apoptosis through an intrinsic mitochondria-mediated apoptotic pathway. Thus, Ir1 exhibited both antimetastatic and antineoplastic properties, indicating that Ir1 may be a viable drug candidate in antimetastasis and anticancer therapies.A novel cyclometalated iridium(III) complex exhibited both antimetastatic and antineoplastic properties by inhibiting the proliferation, migration and invasion of MDA-MB-231 human breast cancer cells.Display Omitted
Keywords: Iridium(III) complex; Invasion; Migration; Antimetastasis; Anticancer;

A pair of novel 2D homochiral coordination polymers based on proline-tetrazole ligand, namely [Cd((S)-PTZ)2]n (1-L) and [Zn((S)-PTZ)2]n (2-L), were obtained and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, solid-state CD spectra, single-crystal X-ray crystallography and powder X-ray diffraction. The compounds 1-L and 2-L display 4-connected net and SHG response.By using proline-tetrazole ligand ((S)-HPTZ) to assemble with Cd2 + (Zn2 +) ions, two homochiral metal–organic frameworks (HMOFs) with 4-connected net have been successfully synthesized.Display Omitted
Keywords: Homochiral coordination polymers; Proline-tetrazole; 4-Connected net;

Synthesis, crystal structure and relevant antiproliferative activity against Toxoplasma gondii of a new binuclear Co(II) complex by Vagner M. de Assis; Lorenzo C. Visentin; Fernanda S. de Souza; Renato A. DaMatta; Adolfo Horn; Christiane Fernandes (47-50).
The crystal structure of [(HPClNOL)Co(-μ-Cl2)Co(HPClNOL)](ClO4)2 1 (HPClNOL: 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol) revealed a distorted octahedral geometry around both Co(II) centers. The coordination plane comprised one tertiary amine, one alcohol in the protonated form and two chloride which link the two Co(II) centers, resulting in the binuclear arrangement. Two pyridine nitrogen atoms are coordinated and occupy the axial sites. Investigations in solid state and in solution (dimethylformamide) carried out by electronic spectroscopy suggest that the arrangement in the solid state changes in solution. Furthermore, ESI(+)-MS and conductivimetry studies indicated the formation of mononuclear species in solution in agreement with the lability of the chloride ligands. Complex 1 reduced the growth of Toxoplasma gondii infecting LLC-MK2 host cells. After treatment this complex reduced T. gondii growth by 55%, the ligand HPClNOL had no effect on parasite growth and sulfadiazine (SDZ), traditional terapeutic compound for this parasite, was effective only after 48 h of treatment. These results suggest the relevance of the cobalt ion on the anti-toxoplasma activity.
Keywords: Cobalt(II) complex; X-ray diffraction studies; ESI(+)-MS; T. gondii; Antiproliferative activity;

Synthesis and thermal stability study of a cobalt-organic framework with tetrahedral cages by Xiao-Ying Lin; Qin-Qin Zheng; Xin-Zhong Liu; Xiao-Yu Jiang; Cheng Lin (51-54).
A new stable cobalt-organic framework, namely [Co2(oba)2(H2Me4bpz)]n (1) (H2oba = 4.4′-oxydibenzoic acid, H2Me4bpz = 3.3′,5,5′-tetramethyl-4,4′-bipyrazole), has been synthesized by combining the mixed H2oba and H2Me4bpz with Co(CH3COO)2·4H2O under solvothermal conditions, which was characterized by infrared spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analyses. Single-crystal X-ray diffraction analysis reveals that 1 features a three-dimensional framework, which is built from interesting tetrahedral cages. The thermal stability of the complex has also been investigated.A new stable metal-organic framework, namely [Co2(oba)2(H2Me4bpz)]n (H2oba = 4.4′-oxydibenzoic acid, H2Me4bpz = 3.3′,5,5′-tetramethyl-4,4′-bipyrazole), has been synthesized and its thermal stability was explored.Display Omitted
Keywords: Mixed ligand; Crystal structure; MOFs; Thermal stability; Cobalt;

New spin crossover polymeric composite and another way to describe the result by Wenping Wang; Bibi Ji; Chen Zhang; Xiaohua Cao (55-59).
Firstly, we synthesized a novel spin crossover coordination compound 1 {[Fe(MPEG-trz)3](BF4)2}(MPEG-trz: polymeric ligand obtained by amidation reaction between methoxy polyethylene glycol (MPEG) and 4-amino-1,2,4-triazole (NH2-trz)). And then a suite of coordination compounds {[Fe(MPEG-trz)m(NH2-trz)n](BF4)2}(m = 2, n  = 1, 2; m = 1.5, n  = 1.5, 3; m = 1, n  = 2, 4;) have been successively synthesized by self-assembly reaction between Fe(BF4)2·6H2O and MPEG-trz/NH2-trz in different proportion respectively. The structure detail is obtained through FT-IR, XRD and 1H NMR measurements, while spin crossover behavior of these coordination compounds are inspected by superconducting quantum interference device (SQUID) and DSC. The new polymeric composites not only show mechanical behavior particular the malleability but also exhibit an abrupt spin crossover behavior with a slender hysteresis loop. Simultaneously we speculated the probably cooperative formation mechanism of spin crossover system on the based of analysis upon the magnetic performance among these coordination compounds with different proportions in MPEG-trz and NH2-trz.The characterization of spin crossover phenomenon for SCO coordination compounds.Display Omitted
Keywords: Spin crossover; Polymeric composite; Malleable; Modification; Cooperative formation mechanism;

Combining solvent-assisted linker exchange and transmetallation strategies to obtain a new non-catenated nickel (II) pillared-paddlewheel MOF by Yan Xu; Ashlee J. Howarth; Timur Islamoglu; Cleiser T. da Silva; Joseph T. Hupp; Omar K. Farha (60-63).
A non-catenated nickel (II) pillared paddlewheel metal-organic framework is synthesized through a combination of solvent-assisted linker exchange and transmetallation. Compared to its isostructural Zn(II) analogue, the nickel (II) pillared paddlewheel metal-organic framework features an enhanced N2 sorption performance. It is notable that the nickel (II)-based metal-organic framework could not (in our hands) be synthesized de novo. The experimental results validate that multiple building-block-replacement (BBR) methods can be utilized to access materials that are challenging to synthesize directly.A new non-catenated nickel (II) pillar-layer metal-organic framework is achieved through the combination of solvent-assisted linker exchange (SALE) and transmetallation.Display Omitted
Keywords: Metal-organic framework; Non-catenated; Post-synthetic modification; Pillared paddlewheel; Transmetallation; Solvent-assisted linker exchange;

The reaction of [ReCl3(MeCN)(PPh3)2] with 2-mercapto-orotic acid (H2moa) in ethanol led to the isolation of the multiply-bridged dimer (μ-Cl)(μ-O)(μ-moa)2[ReIIIReIV(PPh3)]2 (1). The compound has a Re―Re bond distance of 2.5425(7) Å with a formal bond order of 2.5. The dianionic bridging ligands moa2 − coordinate bidentately via a neutral pyrimidine nitrogen and carboxylate oxygen to one Re ion, and monodentately through a thiolate sulfur to the second metal ion. Complex 1 was characterized by FTIR, electronic spectroscopy, cyclic voltammetry, microanalysis and single crystal X-ray diffraction.The reaction of [ReCl3(MeCN)(PPh3)2] with 2-mercapto-orotic acid (H2moa) in ethanol led to the isolation of the multiply-bridged dimer (μ-Cl)(μ-O)(μ-moa)2[ReIIIReIV(PPh3)]2 (1). The compound has a Re―Re bond distance of 2.5425(7) Å with a formal bond order of 2.5. The dianionic bridging ligands moa2 − coordinate bidentately via a neutral pyrimidine nitrogen and carboxylate oxygen to one Re ion, and monodentately through a thiolate sulfur to the second metal ion.Display Omitted
Keywords: Rhenium (III/IV); 2-Mercapto-orotic acid; Chelate-bridged; Multiple bond;

Tetra coordinated copper(II) complex of formula [Cu(L1)(imid)] is synthesized using imidazole and a tridentate O,N,O hydrazone ligand L1 prepared by condensation of 1,1,1-trifluoropentanedione and 4-chlorobenzhydrazide. The ligand and complex are characterized by UV–Visible, FTIR, NMR, mass and single crystal XRD techniques. DNA binding mode is assessed by UV absorption, fluorescence spectral and circular dichroism studies. Based on the results, it is observed that complex has preferred intercalative mode of binding with DNA. The binding constant, K b , was found to be 4.02 ± 0.09 × 104  M− 1. Thermodynamic parameters such as ΔH, ΔS and ΔG obtained from acridine orange fluorescence displacement assay revealed that the hydrophobic and hydrogen bonding interactions are playing a major role in the binding pattern. In addition, cytotoxicity of the complex towards MCF-7 breast cancer cell line has also been assessed.Tetradentate copper(II) complex was synthesized using novel hydrazone ligand and nitrogen donor heterocycle. DNA binding mode of the characterized complex was investigated using UV absorption, fluorescence displacement assays, circular dichroism studies and molecular docking studies. The cytotoxicity of the complex was assessed against MCF-7 cell line.Display Omitted
Keywords: DNA interactions; Cytotoxicity; Copper complex; Hydrazone; Spectroscopic studies;

The selective oxidation of hydrocarbons is a main academic and industrial research challenge. A lot of researches have been done about this issue, but till now relatively little attention has been paid to graphene-complex oxide nanocomposites. Herein, we report our studies on a new catalyst. Silver ferrite–graphene (AgFeO2–G) as a separable nanocomposite from the reaction solution, was used as an effective oxidizing agent for the oxidation of various hydrocarbons (1- decene, cyclohexene, cis-cycloctene, cyclohexane, cyclooctane etc.) under mild conditions (55  C, 8 h) with high conversion and selectivity using air, that is proper for ‘green’ chemistry. Metal or metal oxide nanoparticles assembled on graphene sheets revealed high electrocatalytic activity. Indeed, AgFeO2 with graphene due to low band gap and graphene oxide with large amounts of oxygen-containing groups, provide facility catalytic activity of catalyst-supported system. We also found that, with this catalyst, selective oxidation could be achieved without the need for the addition of solvent, which is appropriate in particular for ‘green’ chemistry. The catalysts showed little deactivation and maintained their conversion and selectivity levels duration of the measurements.Display Omitted
Keywords: Oxidation; Silver; Selective; Nanocomposite; Graphene;

Intramolecular self-alkylation reaction of an iron(II) dichloroclathrochelate caused cyclization–demethylation in its chelate ribbed fragment by Genrikh E. Zelinskii; Alexander S. Belov; Anna V. Vologzhanina; Valentin V. Novikov; Оleg А. Varzatskii; Yan Z. Voloshin (80-84).
Nucleophilic substitution of an iron(II) dichloroclathrochelate precursor FeBd2(Cl2Gm)(BF)2 (where Bd2 − and Gm are α-benzildioxime dianion and glyoxime residue, respectively) with 3-dimethylaminopropylamine unexpectedly afforded the macrobicyclic product of an intramolecular cyclization followed by a demethylation reaction with elimination of CH3Cl. The molecular structure of this clathrochelate was unambiguously confirmed both in solution and in solid state using multinuclear NMR spectroscopy and by single crystal X-ray diffraction, respectively.Nucleophilic substitution of an iron(II) dichloroclathrochelate precursor with 3-dimethylaminopropylamine gave the macrobicyclic product of intramolecular cyclization–demethylation reaction in its ribbed fragment.Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Ligand reactivity; Intramolecular cyclization; Dealkylation reaction;

Syntheses, crystal structures and magnetic studies of new manganese(II) coordination polymers with ditopic N-pyridinylisonicotinohydrazide ligand and dicyanamide by Rahman Bikas; Nader Noshiranzadeh; Lesław Sieroń; Hassan Hosseini-Monfared; Jose Manuel Barandiaran; Tadeusz Lis; Javier Alonso (85-89).
Two new coordination polymers of Mn(II) with dicyanamide anion (dca) and isonicotinohydrazone based ligands, {[Mn2(L1)2(dca)2(CH3OH)2]·H2O}n (1) and [Mn2(L2)2(μ-dca)2]n (2), were synthesized and characterized by elemental analyses and spectroscopic methods where HL1  = (E)-N′-(phenyl(pyridin-2-yl)methylene)isonicotinohydrazide and HL2  = (E)-N′-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide. The IR spectra of 1 and 2 show the characteristic stretching vibration bands of a dicyanamide ligand as three bands. Structures of the compounds were characterized by X-ray diffraction analysis which indicates that the isonicotinohydrazone ligands act as a ditopic ligand and coordinate to manganese ions via the N2O-donor set and pyridine group of the isonicotine part. The magnetic susceptibility measurements studies indicated the presence of an antiferromagnetic coupling between high spin Mn(II) ions. Antiferromagnetic coupling for 2 is stronger than that of 1 which is due to connection of Mn(II) ions through dicyanamide bridges in the former.Syntheses, crystal structures and magnetic properties of two new N-arylideneisonicotinohydrazide Mn(II) coordination polymers with dicyanamide co-ligand are reported.Display Omitted
Keywords: Hydrazone ligands; Magnetic behavior; Coordination polymers; X-ray crystal structures; Manganese polymers;

A novel europium coordination polymer based on mixed carboxylic acid ligands: Synthesis, structure and luminescence by Yi-Ling Sun; Xun Feng; Nan Guo; Li-Ya Wang; Rong-Fang Li; Ruo-Fei Bai (90-94).
A novel europium complex, formulated as {[Eu4(H3Pimda)4 (Himba)2·4H2O]·4H2O}n (1) (H3Pimda = 2-propyl-1H-imidazole-4,5-dicarboxy acid, and Himba = 4-(1H-imidazole-1-ly) benzoic acid), has been obtained by the hydrothermal reaction. Single crystal X-ray diffraction analysis shows that complex 1 exhibits one-dimensional (1-D) ribbon-double chain composed of tetranuclear europium clusters, and these chains are further linked by Himba ligands into the 2-D corrugated layer arrays. Complex 1 exhibits efficiently sensitized red luminescence in visible region in N,N-dimethyl formamide (DMF) based on characterization emission of europium(III) ion. When Cd(NO3)2 is dropped in the DMF suspension of 1, the luminescence intensity increases linearly, rapidly, which indicates it may be employed as a fluorescent ratiometric probe for detection pollutant Cd(II) anion. In addition, complex 1 is characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis and PXRD measurement.A unique europium coordination polymer based on mixed carboxylic acid ligands, {[Eu4(Pimda)4 (Imiba)2·4H2O]·4H2O}n has been synthesized and characterized, 1 may be employed as a fluorescent ratiometric probe for pollutant Cd(II) ion.Display Omitted
Keywords: Europium coordination polymer; 2-Propyl-1H-imidazole-4,5-dicarboxy acid; Tetranuclear {Eu4} cluster; Luminescence property;

Two novel dioxygen heptaoxomolybdates K5[Mo7O22(O2)(OH)]Cl·6H2O (1) and K5[Mo7O22(O2)(O2)]·8H2O (2) were isolated from the solution of peroxo molybdate accidently. The solids were characterized by IR, EPR and X-ray single crystal analysis. Complex 1 contains a superoxo group with a short bond distance 1.27(1) Å, while 2 is a mixed complex with peroxo and superoxo groups [1.43(1), 1.27(1) Å]. All of the dioxygen groups coordinate to molybdenum atoms in side-on (η2) fashion. The two complexes are short-lived and will decompose into peroxo molybdates K5[Mo7O21(O2)2(OH)]·6H2O (3) and K6[Mo7O22(O2)2]·9H2O (4) very quickly.Novel superoxo/peroxo heptaoxomolybdates were isolated from the solution of peroxo molybdate accidently, which decompose into peroxo molybdates very quickly. Both complexes 1 and 2 contain a superoxo group with a short bond distance 1.27(1) Å in side-on fashion.Display Omitted
Keywords: Molybdate; Superoxo; Peroxo; Hydrogen peroxide; Catalysis;

A new cyanide-bridged CrIII ―CoII heterometallic complex {[Co(L-N5)]3[Cr(CN)6]2}n·nCH3CN·5nH2O (1) has been synthesized by the reaction of [CoII(L-N5)2(H2O)2]·(ClO4)2 with the hexacyanidechromate(III) building block K3[CrIII(CN)6]. X-ray single crystal diffraction analysis shows that complex 1 has a two-dimensional (2D) layer-like structure. Magnetic investigations show that the magnetic coupling between Cr(III) and Co(II) ions through cyanide bridge is ferromagnetic for the complex. The complex displays typical soft ferromagnet behaviors with a three-dimensional ferromagnetic ordering of T c  = 15.0 K, a small coercive field of 10 Oe and a remnant magnetization of about 7.8 Nβ.A new cyanide-bridged two-dimensional CrIII ―CoII complex has been synthesized. Magnetic property investigations show that the complex is a typical ferromagnetic with T c  = 15.0 K.Display Omitted
Keywords: Cyanide-bridged; Heterometallic; Layer-like structure; Ferromagnet;

A novel octa-nuclear cerium(III)-containing organic-inorganic hybrid polyoxometalate [N(CH3)4]8H16[{Ce(η 1-C6H5NO2)2(H2O)6[Ce(H2O)3(α 2-P2W17O61)]}{Ce(η 2-C6H5NO2)2(H2O)5[Ce(H2O)(α 2-P2W17O61)]}]2·90H2O (C6H5NO2  = isonicotinic acid) (1) was obtained, which had been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Structural analysis indicated at 1 is composed of four lacunary Dawson-type units [α 2-P2W17O61]10 − joined together by eight cerium cations forming an uncommon zigzag tetrameric structure with eight isonicotinic acids as the organic pendants coordinating to the cerium cations. Magnetic property studies indicate that obvious antiferromagnetic interactions exist in eight Ce3 + cations.A novel octa-nuclear cerium(III)-containing organic-inorganic hybrid tetrameric polyoxometalate based on monovacant Dawson-type units [α 2-P2W17O61]10 − with eight isonicotinic acids as pendants has been synthesized and characterized.Display Omitted
Keywords: Organic-inorganic hybrid; Monovacant Dawson; Polyoxometalates; Lanthanide;

Water soluble luminescent cyclometalated platinum(II) complex — A suitable probe for bio-imaging applications by Sheik Saleem Pasha; Pradip Das; Nigam P. Rath; Debashree Bandyopadhyay; Nikhil R. Jana; Inamur Rahaman Laskar (107-111).
A highly water soluble platinum(II) complex, [Pt(ppy)(en)]Cl, (where ppy = 2-phenylpyridine and en = ethane-1, 2-diamine) with a strong green luminescence in solution was synthesized in two steps. Initially, an intermediate complex, [Pt(ppy)(ppyH)(Cl)], 1 was isolated which was transformed into the light-emitting mononuclear platinum(II) complex, [Pt(ppy)(en)]Cl, 2. The green emission of 2 was changed into yellow in their solid state. The strong ππ intermolecular interactions that interplays between the phenyl rings lying into the two consecutive molecules which led to the solid state emission. The low cytotoxicity of 2 ensures the feasibility for using these in bioimaging probe. The testing bioimaging results demonstrate that the compound penetrates the cell membrane in both cancer (HeLa, U87MG and Nuro2a) and normal cells (CHO-K1 and 3T3-L1). The cellular uptake was observed to much higher in cancerous cells only. Co-localization study confirmed the localization of it into the cell nucleus.Synthesized compound is highly water soluble, Low toxic and selectively stain the nucleus of cancerous cells.Display Omitted
Keywords: Platinum complex; Bio-imaging; Luminescence; Toxicity;