Inorganic Chemistry Communications (v.29, #C)

Contents List (iii-xvi).

A novel non-symmetric aliphatic benzamidinato zirconium complex, [{CyNC(Ph)(NSiMe3)}2ZrCl2] (Cy = cyclohexyl) (1) has been readily prepared via the reaction of freshly prepared aliphatic lithium benzamidinate with zirconium tetrachloride. Complex 1 has been characterized by various spectroscopic techniques, elemental analysis, and single-crystal X-ray diffraction analysis. Complex 1 has a distorted pseudo-octahedral structure. Catalytic studies showed that the zirconium complex was active for ethylene polymerization with the activity of 6.66 × 104  g PE/mol Zr h. The influences of Al/Zr molar ratios, ethylene pressures and reaction temperature on the activities were investigated.A novel non-symmetric aliphatic benzamidinato zirconium complex [{CyNC(Ph)(NSiMe3)}2ZrCl2] (Cy = cyclohexyl) (1) has been prepared and characterized. Complex 1 was found to be active for ethylene polymerization.Display Omitted► A novel non-symmetrical aliphatic zirconium benzamidinate was prepared. ► The complex has been characterized by single crystal X-ray diffraction. ► The catalytic behaviors of the complex were investigated.
Keywords: Aliphatic benzamidinato ligand; Bis(amidinate) zirconium complex; Synthesis; Structure; Polymerization of ethylene;

Auxiliary ligand-directed synthesis of four novel functional supramolecular metal–organic frameworks from 1-D chains to 3-D architectures by Chu-Jun Chen; Xiao-Ping Ye; Jin-Ying Gao; Wei-Ping Xie; Xing-Rui Ran; Shan-Tang Yue; Yue-Peng Cai (4-10).
Four novel functional supramolecular metal–organic coordination polymers, [Cd2Cl3(IP)2(NIPH)2](1), [Zn2(IP)22-SO4)2(NIPH)2]·2H2O(2), [Cd(IP)2(BPDC)](3), [Zn2(IP)2(NDC)2](4) (IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline, H2NIPH = 5-nitro-isophthalic acid, H2BPDC = 4,4′-biphenyldicarboxylic acid, H2NDC = 2,6-naphthalenedicarboxylic acid), have been obtained through three types of dicarboxylate linkers. All the four compounds are extended into a 3-D supramolecular framework by hydrogen bonds or weak aromatic interactions. The different structures demonstrate the effect of the dicarboxylate ligands on the formation of such coordination architectures. Compound 1 is a 1-D double-stranded loop-like chain with repeated [Cd4(Cl)4]4 + units connected by H2NIPH ligands. In compound 2, there are two indie 1D zigzag chains jointed by sulfate anions with μ2-bridging mode. With different metal centers, compounds 1 and 2 hold different crystal structures. With different auxiliary dicarboxylate ligands, compounds 3 and 4 exhibit disparate 1D chains. The fluorescence property and thermal stability of all complexes are also investigated.The synthetic route of complexes 14.Display Omitted► All compounds exhibit 3D supramolecular net with intermolecular weak interactions. ► With different metal centers, compounds 1 and 2 possess different crystal structures; ► With different auxiliary ligands, compounds 3 and 4 exhibit disparate 1D chains.
Keywords: Transition metals; Dicarboxylato ligand-directed; Hydrogen bonding; Supramolecular architecture; Luminescence;

This communication describes a new (3,8)-connected microporous heterometallic coordination polymer, [Zn2Sr(pbdc)3(μ 2-O1w)2(DMF)]n·n(DMF) (1 H2pbdc = terephthalic acid, DMF =  N,N′-dimethylformamide). Crystallographical analysis reveals that it features an unusual heterometallic trinuclear building unit [Zn2Sr(COO)4(μ 2-OH2)]. These trinuclear clusters are further interconnected by pbdc ligands, giving rise to the final three-dimensional (3D) microporous framework. In 1, DMF molecules not only act as terminal ligands but also act as templates filling in the one-dimensional (1D) channel further consolidating the whole framework. Moreover, this compound also exhibits strong ligand-centered violet luminescence at room temperature in the solid state.Presented here is a new (3,8)-connected microporous heterometallic coordination polymer [Zn2Sr(pbdc)3(μ 2-O1w)2(DMF)]n·n(DMF) (1 H2pbdc = terephthalic acid, DMF =  N,N′-dimethylformamide), which features an unusual heterometallic trinuclear cluster [Zn2Sr(COO)4(μ 2-OH2)] as building subunit.Display Omitted► New microporous heterometallic compounds templated by organic molecule ► New (3,8)-connected topological net ► Intense violet luminescence at room temperature
Keywords: Heterometallic compound; Trinuclear cluster; Template; Luminescence;

Cobalt(II) tetraphenyltetranaphthoporphyrin, with extended conjugation at the pyrrole units, has been synthesized and its spectroscopic and electrocatalytic behavior toward the reduction of oxygen has been investigated. The new complex shows a red shift for the Soret band of 75 nm compared to its cobalt(II) tetraphenylporphyrin analog. In addition, the new complex shows enhanced electrocatalytic ability for the reduction of oxygen in acidic media converting over 50% of the oxygen directly to water, a four electron process at relatively high potentials.Cobalt(II) inserted into a highly conjugated porphyrin macrocycle displays red-shifted electronic transitions and an enhanced electrocatalytic ability toward the reduction of oxygen in acidic media when compared to its less conjugated analog cobalt(II) tetraphenylporphyrin.Display Omitted► A new cobalt(II) porphyrin with extended p-conjugation has been synthesized. ► The new metal complex and its free-base porphyrin have red-shifted electronic spectra. ► New cobalt complex shows enhanced electrocatalysis of oxygen in acidic solutions.
Keywords: Electrocatalysis; Oxygen reduction; Fused-pyrrole; Cobalt porphyrin;

Photoluminescent and ferroelectric properties of a chiral rhenium(I) complex based on the chiral (−)-4,5-pinene-2,2′-bipyridine ligand by Yong-Hui Zhou; Jun Li; Tao Wu; Xiao-Peng Zhao; Qiu-Lei Xu; Xi-Li Li; Ming-Bo Yu; Li-Li Wang; Peng Sun; You-Xuan Zheng (18-21).
A rhenium(I) complex ReL R,R (CO)3Cl (1) based on a chiral ligand, L R,R  = (−)-4,5-pinene-2,2′-bipyridine [(6R)-5,6,7,8-tetrohedro-7,7-dimethyl-3-(2-pyridinyl)-6,8-methanoisoquinoline], was synthesized and characterized. The emission spectrum of 1 shows efficient dπ(Re) → π* (diimine) (MLCT) phosphorescence with a photoluminescence quantum efficiency of 0.035. The excited state lifetimes of Re(I) complex, measured in CH2Cl2 solution (1.82 μs) and solid state (2.15 μs) at room temperature, support the hypothesis of the MLCT character of the emitting state. Single crystal X-ray diffraction analyses show that complex 1 crystallizes in the chiral space group P21 of monoclinic system. The PE hysteresis loop indicates its obvious ferroelectricity with the remnant polarization (P r) value of 0.17 μC/cm2 at an applied field of 4.8 kV/cm. To the best of our knowledge, complex 1 represents the first rhenium-based complex reported with ferroelectricity.A new chiral rhenium(I) complex was synthesized and structurally characterized, which shows photoluminescent and ferroelectric properties and represents the first example of rhenium-based complex with ferroelectricity.Display Omitted► A new chiral rhenium(I) complex with crystal structure characterization ► Displaying photoluminescent and ferroelectric properties. ► Representing the first rhenium-based example with ferroelectricity
Keywords: Rhenium(I) complex; Chirality; Photoluminescence; Ferroelectricity;

A new tetranuclear nickel complex based on the benzimidazole ligand for the controllable polymerization of methyl methacrylate by Qi Shi; Leilei Chen; Dengfeng Liu; Jing Wu; Liying Wu; Luqun Zhu; Qingqiang Cheng; Rong Lu; Daidi Fan; Xingqiang Lü (22-26).
The new tetranuclear [Ni4(L)6Cl]⋅ Cl (1) complex from the benzimidazole-based ligand HL (HL: 2-(1H-benzo[d]imidazol-2-yl)-6-methoxyohenol) was prepared and structurally characterized by EA, FT-IR and X-ray single-crystal diffraction. The tetranuclear complex 1 was shown to efficiently catalyze the controllable polymerization of methyl methacrylate (MMA) in activation with AIBN (azobisisobutyronitrile), giving the syndio-enriched atactic PMMAs. The existence of two active species in the 1/AIBN systems should be favorable for the higher catalytic activities, while the cooperative interactions between the two active centers should result in the relatively broad molecular weight distributions for the obtained PMMAs.The obtained new tetranuclear [Ni4(L)6Cl]⋅ Cl (1) complex from the benzimidazole-based ligand HL (HL: 2-(1H-benzo[d]imidazol-2-yl)-6-methoxyohenol) was shown to efficiently catalyze the controllable polymerization of MMA in activation with AIBN, giving the syndio-enriched atactic PMMA. The existence of two active species in the 1/AIBN systems should be favorable for the higher catalytic activities, while the cooperative interactions between the two active centers should result in the relatively broad molecular weight distribution for the obtained PMMAsDisplay Omitted► Tetranuclear Ni2 + complexes assembled from the benzimidazole-based ligand ► Controllable polymerization of MMA ► Two active species and their cooperative interaction
Keywords: Tetranuclear cationic nickel complex; Benzimidazole-based ligand; Controllable polymerization of methyl methacrylate; Two active species and their interaction;

One new title compound [Cu2(TPOM)(adi)2] n  · 4nH2O (1) (TPOM = tetrakis(4-pyridyloxymethylene)methane, adi = adipic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction.One new compound [Cu2(TPOM)(adi)2] n  · 4nH2O has been synthesized under hydrothermal condition. The compound has a 3-fold interpenetrating 3D architecture.Display Omitted► A new Cu coordination polymer with mixed-ligands has been synthesized. ► The 3D framework was proved by single-crystal X-ray diffraction. ► Title polymer is an interesting 3-fold interpenetrated 3D structure.
Keywords: Flexible tetrapyridine; Fatty acid ligand; Crystal structure; Coordination polymer;

Triangular {Mn(OH)}3 6 + fragment encapsulated in trivacant [A-R-SiW9O34]10 − ligand by Na Zhang; Bin Liu; Xue-Mei Liu; Tuo Ding; Yan-Yan Jia; Gang-Lin Xue (30-32).
[{MnIII(OH)(H2O)}3SiW9O34]4 − 1a, has been isolated from the reaction of Na9[β-SiW9O34H]·23H2O and [Mn3O(O2CMe)6(HIm)3](O2CMe) (Im = imidazole C3H4N2) in aqueous solution. The trimetal-substituted polyoxometalate (TMSP) 1 has been fully characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and infrared spectroscopy. This monomeric anion is composed of one trilacunary Keggin fragment A-α-SiW9O34 and three manganese ions encapsulated resulting in a triangular {Mn(OH)}3 6 + ring core. Experimental structural and magnetism aspects of the material are reported and discussed.A new complex displays trilacunary Keggin ligand [A-α-SiW9O34]10 − encapsulating triangular {Mn(OH)}3 6 + fragment, in which hydroxo bridges connect the high-spin Jahn–Teller (JT) distorted MnIII centers with antiferromagnetic coupling predominates throughout the cluster.Display Omitted► {Mn(OH)}3 6+ encapsulated in trivacant Keggin anion SiW9O34 10− was obtained ► Magnetism measurement convinced spin frustration in the Mn3 core ► Mn ions in complex 1 show evident Jahn–Teller (JT) distortion
Keywords: Polyoxometalates; Silicotungstate; Lacunary Keggin; Manganese; Magnetism;

Synthesis, characterization and catalytic activity of a new sandwich-type tungstophosphate functionalized by carboxyethyltin by He Yang; Lan-Cui Zhang; Liu Yang; Xiao-Lan Zhang; Wan-Sheng You; Zai-Ming Zhu (33-36).
Reaction of the trivacant Keggin-type tungstophosphate (A-α-Na9PW9O34⋅ 7H2O, abbreviated as {PW9}) with estertin (Cl3Sn(CH2)2COOCH3) in an acetate buffer solution leads to the formation of a new sandwich-type tungstophosphate functionalized by carboxyethyltin, Na3K8[K3{Sn(CH2)2COO}2(A-α-PW9O34)2]·18H2O (1). The title compound was characterized by single crystal X-ray diffraction, elemental analysis, IR, TG, PXRD, 13C, 31P and 119Sn NMR. Structural analysis reveals that the basic skeletal structure of 1 is made up of two [Sn(CH2)2COO]2 + groups and three K+ ions sandwiched by two A-α-[PW9O34]9 − building blocks, which shows the original estertin precursors hydrolyzed into carboxyethyltin. The catalytic activity of 1 has been investigated.A new sandwich-type tungstophosphate functionalized by carboxyethyltin groups has been synthesized, and it shows better catalytic activity.Display Omitted► The estertin derivatives is firstly linked to the A-α-[PW9O33]9 − skeletons. ► 1 formed in aqueous solution and has been characterized by NMR. ► 1 has a good electrocatalytic activity towards the reduction of H2O2. ► 1 was used as a catalyst for the oxidation of cyclohexanol to cyclohexanone.
Keywords: Sandwich-type tungstophosphate; Estertin; Functionalization; Catalytic activity;

A hexanuclear metallacrown palladium(II) cluster derived from 2-mercaptoethanol by Kamran T. Mahmudov; Xudayar I. Hasanov; Abel M. Maharramov; Asmat N. Azizova; Karim Q. Ragimov; Rizvan K. Askerov; Maximilian N. Kopylovich; Zhen Ma; Armando J.L. Pombeiro (37-39).
A [12]metallacrown-6 palladium cluster, [Pd6(μ 2-SCH2CH2OH)12] (1), was obtained upon reaction of Pd[(NH3)4]Cl2 with 2-mercaptoethanol in water solution. 1 was characterized by IR spectroscopy, elemental and single crystal X-ray diffraction analyses. Within the molecule, the six palladium atoms are united by disulfobridges (from twelve thiolate anions), forming almost ideal plane hexagon. Each palladium is surrounded by four sulphur atoms in an approximately square planar fashion, with Pd–S distances of 2.3094(5)–2.3378(5) Å, while the shortest Pd–Pd distance is 3.0931(2)–3.1098(2) Å. The clusters are interconnected by hydrogen bonds through hydroxy-groups of thiolate ligands forming a supramolecular infinite 3D structure.In a hexanuclear metallacrown palladium(II) cluster, each Pd atom is surrounded by four S atoms of the μ 2-SCH2CH2OH ligands in a distorted square-planar fashion.Display Omitted► A hexanuclear metallacrown palladium(II) cluster. ► The six Pd(II) atoms possess nearly virtual C 6 symmetry. ► The X-ray structure of the [Pd6(μ 2-SCH2CH2OH)12] was described.
Keywords: Palladium cluster; 2-Mercaptoethanol; Crystal structure;

Oxidation of olefins with tert-butyl hydroperoxide (TBHP) catalyzed by carbon nanotube supported iron(III) and manganese(III) complexes of meso-tetrakis(4-hydroxyphenyl)porphyrin is reported. The results show higher catalytic activity of the Fe(III) complex compared to the Mn(III) one. With the exception of cyclooctene which gives cyclooctene oxide as the sole product, oxidation of styrene, α-methyl styrene and cyclohexene leads to the formation of benzaldehyde, acetophenone and cyclohexene-1-one as the major product, respectively. In this study, acetonitrile has been found to be the best solvent for reaction performed in the presence of the manganese and iron porphyrin. In comparison of the two metalloporphyrins, catalytic activity of the manganese porphyrin is more sensitive to the type of solvent than the iron one. In spite of the crucial role of imidazole (ImH) on catalytic performance of the manganese porphyrin, the presence of ImH has a negative effect on the activity of the iron porphyrin. The nano-tube supported iron porphyrin may be recovered and reused at least four times without significant loss of the catalytic activity.Carbon nano-tube supported iron meso-tetrakis(4-hydroxyphenyl)porphyrin has been found to show higher catalytic activity in oxidation of olefins with tert-butyl hydroperoxide compared to the manganese counterpart. Also the nano-tube supported iron porphyrin may be recovered and reused at least for four times without significant loss of the catalytic activity.Display Omitted► Carbon nanotube supported iron(III) and manganese(III) porphyrins ► A heterogeneous catalyst was prepared. ► These catalysts were used in the oxidation of alkenes with TBHP. ► Makes the catalyst reusable
Keywords: Porphyrin; Heterogeneous catalyst; Carbon nanotube; Olefin; Oxidation;

Weakley sandwich-type anion in organic–inorganic hybrid compound with 3D framework by Chun-Hua Zhang; Ya-Guang Chen; Shu-Xia Liu (45-48).
Reaction of Na2WO4·2H2O, GeO2, Cu(Ac)2·H2O and H4EGTA in conventional conditions results in formation of a new compound, (H3O)4Cu(H2O)6[K6(H2O)17Cu2(EGTA)(H2O)2{Cu4(H2O)2(B-α-GeW9O34)2}]·9H2O (1) (EGTA = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetate tetraanion). Its crystal structure was determined with X-ray diffraction method. The in situ synthesized [Cu4(H2O)2(B-α-GeW9O34)2]12 − has the typical Weakley sandwich structure and acts as an eleven-dentate ligand linking nine K+ ions and two Cu2 + ions. All Cu2 + ions are in an elongated octahedral environment. Two Cu2 + ions are chelated by EGTA from two ends and coordinated by terminal oxygen atoms of [Cu4(H2O)2(B-α-GeW9O34)2]12 −, forming a chain CuEGTA-Cu4(H2O)2(GeW9O34)2. K+ ions connect the chains into a complicated three dimensional framework. The magnetic measurement shows that 1 exhibits antiferromagnetic property.Weakley sandwich-type anion [Cu4(H2O)2(B-α-GeW9O34)2]12 − was in situ synthesized and acts as an eleven-dentate ligand linking nine K+ ions and two Cu2 + ions in (H3O)4Cu(H2O)6[K6(H2O)17Cu2(EGTA)(H2O)2{Cu4(H2O)2(B-α-GeW9O34)2}]·9H2O (1), which is the highest dentate number for the anion. [Cu4(H2O)2(B-α-GeW9O34)2]12 −, Cu2 + ions and EGTA are assembled into a complicated 3D framework with antiferromagnetic property.Display Omitted► [Cu4(H2O)2(B-α-GeW9O34)2]12 − was in situ synthesized in presence of H4EGTA. ► [Cu4(H2O)2(B-α-GeW9O34)2]12 − acts as an eleven-dentate ligand in the compound. ► The chelating ligand EGTA plays an important role in constructing 3D framework. ► 1 is first structurally-defined compound of [Cu4(H2O)2(GeW9O34)2]12 − and Cu-EGTA.
Keywords: Sandwich-type polyoxometalate; Tungstogermanate; Polyaminopolycarboxylic acid; Conventional synthesis; Magnetic property;

Two organic–inorganic hybrid compounds with the formula {[MnIII(Salen)(H2O)]4MoO4}·Cl2·16H2O (1) and {[MnIII(Salen)(H2O)]4WO4}·(CH3COO)2·11H2O (2) (Salen = Di-[2-hydroxyl-3-methoxyl-benzaldehyde] ethylenediamine) have been synthesized and structurally characterized by IR, UV–vis spectroscopy, TG analysis and single crystal X-ray diffraction. Structural analysis revealed that compounds 1 and 2 consist of a [MoO4]2 − or [WO4]2 − building unit and four {[MnIII(Salen)(H2O)]+ metal–organic moieties, respectively. In the crystal structure, the [MoO4]2 − or [WO4]2 − tetrahedra coordinated with four MnIII ions, resulting in the penta-nuclear heterometallic tetrahedra cluster compounds, which were rarely observed in the Mn-Salen system. Magnetic study revealed that there was antiferromagnetic coupling in the two compounds.A penta-nuclear {MMn4} (M = W and Mo) heterometallic clusters with four Mn-Salens exhibit the tetrahedron structural and a 3D supramolecular porous framework.Display Omitted► Two penta-nuclear {MMn4} heterometallic clusters are both tetrahedral structure. ► Compounds 1 and 2 are both based on four Mn-Salens. ► Compounds 1 and 2 both exhibit a 3D supramolecular porous framework.
Keywords: Schiff base; Heterometallic cluster; Manganese; Magnetic properties;

When [PtIV(NH3)5Cl]3 + is deprotonated the complex [PtIV(NH3)4(NH2)Cl]2 + is formed. Upon NH2  → PtIV LMCT excitation (λ irr  > 250 nm) a reductive elimination takes place: [PtIV(NH3)4(NH2)Cl]2 +  → [PtII(NH3)3Cl]+  + N2H4  + H+. Since Pt(II) ammine complexes can be reoxidized to Pt(IV) by H2O2 it is suggested that in a cyclic process the overall reaction could proceed according to the equation: 2 NH3  + H2O2  → N2H4  + 2 H2O.Display Omitted► The complex [PtIV(NH3)4(NH2)Cl]2+ shows an (amide to PtIV) LMCT absorption. ► Upon LMCT excitation a reductive elimination occurs. ► The photolysis yields [PtII(NH3)3Cl]+ and hydrazine.
Keywords: Coordination chemistry; Platinum; Photochemistry; Hydrazine;

The new anion [Cr2(CO(NH2)2)2(C6H4O7)2]2 − has been isolated in the complex [Cr(CO(NH2)2)6]2[Cr2(CO(NH2)2)2(C6H4O7)2]3. The crystals of this complex were obtained by a one-pot synthetic method using 1:1 molar ratio of hexaureachromium(III) chloride and trisodium citrate in aqueous medium. It was characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction analysis. The compound crystallizes in space group R‾3 of the trigonal system with three formula units in a cell of dimensions a  =  b  = 24.7461(4) Å, c  = 13.7204(3) Å and γ = 120°. The crystal structure comprises the columns consisting of [Cr(CO(NH2)2)6]3 + cations surrounded by a cylinder of complex anions, [Cr2(CO(NH2)2)2(C6H4O7)2]2 − which are packed in a honeycomb-like manner. This supramolecular architecture is formed and stabilized by inter- and intramolecular N―H⋯O hydrogen bonds.A new anion [Cr2(CO(NH2)2)2(C6H4O7)2]2− has been isolated by using the one-pot synthetic method. The crystal structure comprises the columns consisting of [Cr(CO(NH2)2)6]3+ cations surrounded by a cylinder of [Cr2(CO(NH2)2)2(C6H4O7)2]2– anions. Such columns are packed in a distinctive honeycomb-like pattern. This supramolecular architecture is stabilized by inter- and intramolecular N―H…O hydrogen bonds.Display Omitted► A new anion, [Cr2(CO(NH2)2)2(C6H4O7)2]2– has been isolated by a one-pot synthesis. ► Crystal structure reveals the presence of both inter and intramolecular H-bonds. ► Crystals are packed in a distinct honeycomb like pattern.
Keywords: Chromium(III); Coordination chemistry; One pot synthesis; Spectroscopy; X-ray crystallography;

The synthesis and characterisation of magnetic nanoparticles and their interaction with a zinc phthalocyanine by Edith Antunes; Nomasonto Rapulenyane; Mpho Ledwaba; Christian Litwinski; Wadzanai Chidawanyika; Tebello Nyokong (60-64).
A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised.FePt nanoparticles (NPs) with Fe (2) or Pt as the shell (3), Pt NPs (4), and FePd NPs (5) were synthesised. Their effect on the UV/Vis absorption and fluorescence spectra of a zinc phthalocyanine (ZnPc) was studied. Nanocomposites (NCs, 6,7), with ZnPc as the stabiliser, were also synthesized and studied.Display Omitted► A range of magnetic nanoparticles were synthesized and characterized. ► Zinc phthalocyanine (ZnPc) ligand exchange was accomplished. ► ZnPc was successfully employed as a stabilizer for NP synthesis. ► Significant Q band red shifting observed in the UV/Vis and fluorescence spectra.
Keywords: Tetra-substituted pyridyl-oxy zinc phthalocyanine; Magnetic nanoparticles; Pt nanoparticles; Phthalocyanines as stabilisers;

Methyl transfer reaction between MeI and Ni(PPh2CH2CH2SEt)2 complex. A DFT study by Patrycja Sitek; Maria Jaworska; Piotr Lodowski; Aleksandra Chmielowska (65-69).
Density functional theory (DFT/BP86) and the Polarizable Continuum Model (PCM/acetonitrile) for solvation have been applied to investigate the methyl transfer reaction from CH3I to Ni(PPh2CH2CH2SEt)2. Two different mechanisms were considered: SN2 and radical one. The reaction paths for both examined mechanism were determined, and the geometries of possible substrates and products were compared.Density functional theory with the nonhybrid BP86 functional and the polarized continuum model for solvation have been applied to investigate the methyl transfer reaction from CH3I to Ni(PPh2CH2CH2SEt)2. Two different mechanisms were considered: SN2 and radical one. Computational study has shown that the reaction proceeds in accordance with SN2 mechanism.Display Omitted► Two different mechanisms of reaction are studied: S N 2 and radical one. ► The reaction paths for both mechanisms were determined with the DFT/BP86 method. ► Results show that the reaction of Ni(PS)2 with CH3I can be described as S N 2 type.
Keywords: Nickel; SN2; Radical mechanism; DFT; Methyl transfer;

Spacer length effect on the formation of different zinc coordination polymers of 1,4-benzenedicarboxylate and flexible bipyrazolyl ligands by Ming Dai; Lian-Wen Zhu; Ju-Hua Yang; Hong-Xi Li; Min-Min Chen; Zhi-Gang Ren; Jian-Ping Lang (70-75).
The solvothermal reactions of Zn(NO3)2∙6H2O with 1,4-benzenedicarboxylic acid (1,4-H2bdc) and 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)butane (dmpzb) or 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)hexane (dmpzh) afforded two three-dimensional coordination polymers [Zn3(1,4-bdc)3(dmpzb)] n (1) and [Zn2(1,4-bdc)2(dmpzh)] n (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compound 1 has an 8-connected 3D net (a 364185262 Schläfli symbol) assembled from trinuclear [Zn3(1,4-bdc)3] units and 1,4-bdc and dmpzb bridges. Compound 2 has a 6-connected 3D net (with a 485463 Schläfli symbol) constructed from binuclear [Zn2(1,4-bdc)2] units and 1,4-bdc and dmpzh linkers. The solid state luminescent and thermal stability properties of 1 and 2 at ambient temperature were also investigated. The results showed that the spacer lengths of bipyrazol-based ligands did affect the topological structures of zinc(II) coordination polymers.Two 3D coordination polymers [Zn3(1,4-bdc)3(dmpzb)] n and [Zn2(1,4-bdc)2(dmpzh)] n were generated from solvothermal reactions of Zn(NO3)2∙6H2O with 1,4-benzenedicarboxylic acid (1,4-H2bdc) and 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)butane (dmpzb) or 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)hexane (dmpzh). Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Display Omitted► Solvothermal reactions of Zn2 +, 1,4-H2bdc and dmpzb or dmpzh gave two polymers. ► Compound 1 has a 3D net assembled from [Zn3(1,4-bdc)6] units and dmpzb linkers. ► Compound 2 has a 3D net assembled from [Zn2(1,4-bdc)4] units and dmpzh linkers. ► Spacer length effect exerts an impact on the structures of the coordination polymers.
Keywords: Solvothermal synthesis; Zinc complexes; Crystal structures; Spacer length effect; Bipyrazolyl ligand; Luminescence;

Synthesis, characterization and properties of chiral and non-chiral coordination polymers in a zinc 2-(pyridine-3-yl)-1H-imidazole-4, 5-dicarboxylic acid system by Linyan Yang; Lingfei Zeng; Wen Gu; Jinlei Tian; Shengyun Liao; Ming Zhang; Xiaohua Wei; Liangliang Xin; Xin Liu (76-81).
Three different structural metal-organic frameworks (MOFs), [Zn(HPIDC)]n (1), {[Zn3(PIDC)2(H2O)3]·0.5H2O}n (2), and [Zn(HPIDC)(H2O)]n (3), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, circular dichroism spectrum, and thermogravimetric analysis (H3PIDC = 2-(pyridine-3-yl)-1H-imidazole-4, 5-dicarboxylic acid). Single crystal X-ray diffractions show that ligands H3PIDC are doubly deprotonated in complexes 1 and 3, while ligand H3PIDC is triply deprotonated in complex 2. The doubly deprotonated HPIDC2 − coordinates in the μ3 mode to generate 3D or 2D MOFs, displaying two coordination modes. The triply deprotonated HPIDC3 − coordinates in the μ4 mode to generate a 3D MOF. In 1 a (10^3) metal organic net was fabricated (srs SrSi2 topology). In 2, however, a ({6.8^2}{6^2.8^2.10^2}) framework was formed. In 3 a (8^2.10) metal organic net was fabricated. Complexes 1 and 3 are crystallized in the orthorhombic, a chiral space group (P212121). Complex 3 is a chiral compound. Solid-state fluorescence emission spectra: complex 1 shows stronger luminescence than complexes 2 and 3. Absolute quantum yield of complex 2 is 3.60%, which is larger than that of the ligand by more than almost 1.7 folds.Three different structural metal-organic frameworks (MOFs), [Zn(HPIDC)]n (1), {[Zn3(PIDC)2(H2O)3]·0.5H2O}n (2), and [Zn(HPIDC)(H2O)]n (3), were hydrothermally synthesized. Complexes 1 and 3 are crystallized in the orthorhombic, a chiral space group (P212121). Complex 3 is a chiral compound.Display Omitted► Three different structural complexes have been synthesized. ► Complexes 1 and 3 crystallized in the orthorhombic, a chiral space group (P212121). ► Complex 3 is a chiral compound. ► Complex 1 shows stronger luminescence than complexes 2 and 3.
Keywords: 2-(pyridine-3-yl)-1H-imidazole-4, 5-dicarboxylic acid; Circular dichroism spectrum; Luminescent;

1D coordination polymer with octahedral and square-planar nickel(II) centers by Manas Sutradhar; M. Fátima C. Guedes da Silva; Dmytro S. Nesterov; Julia Jezierska; Armando J.L. Pombeiro (82-84).
Synthesis of an interesting Ni(II) 1D-chain, [Ni3(ashz)2(DMF)2(H2O)2]n·4DMF (1·4DMF), derived from N-acetylsalicylhydrazide (H3ashz) has been reported. The unprecedented bridging coordination mode involving the phenoate oxygen of ashz3 − leads to the formation of a polynuclear 1D-chain without any additional spacer ligand. The coordination polymer 1 contains the Ni(II) cations in octahedral and in square-planar environments and shows antiferromagnetic interactions.An interesting 1D coordination polymer, [Ni3(ashz)2(DMF)2(H2O)2]n, bearing octahedral and square-planar Ni(II) environments with an unprecedented coordination mode of N-acetylsalicylhydrazide, is reported.Display Omitted► A new octahedral and square-planar nickel(II) 1D polymer is reported. ► A deprotonated N-acetylsalicylhydrazide (ashz3 −) builds the 1D chain. ► ashz3 − shows an unprecedented coordination mode in this complex. ► The Ni(II) centers are antiferromagnetically coupled.
Keywords: Nickel coordination polymer; N-acetylsalicylhydrazide; 1D chain; Antiferromagnetic interaction; X-ray crystallography;

A MnII 5 tetragonal pyramid stabilized by p-tert-butylcalix[8]arene: Synthesis, structure and magnetic property by Shangchao Du; Hongshan Ke; Yanfeng Bi; Huaqiao Tan; Yang Yu; Jinkui Tang; Wuping Liao (85-88).
A compound, [Mn5(H4C8A)(OH)2(C3H6NO2)(DMF)5(CH3O)1.5(HCO2) (C2H3O2)0.5]·2DMF·CH3OH (1) (H8C8A =  p-tert-butylcalix[8]arene, DMF =  N,N′-dimethylformamide), was synthesized by the solvothermal method in the mixed CH3OH/DMF (1:1) solvent. Compound 1 is featured with a tetragonal pyramid-like MnII 5 cluster encircled within a calix[8]arene molecule with a ‘pleated loop’ conformation. Magnetic study indicates that the MnII centers exhibit antiferromagnetic interactions.A novel Mn5-calix[8]arene compound was obtained by the solvothermal method. This compound is featured with a tetragonal pyramid-like MnII 5 cluster encircled within a calix[8]arene molecule with a ‘pleated loop’ conformation. Magnetic study indicates that the MnII centers exhibit antiferromagnetic interactions.Display Omitted► A tetragonal pyramid-like MnII 5 cluster was obtained with p-tert-butylcalix[8]arene. ► The calix[8]arene molecule adopts a ‘pleated-loop’ conformation. ► The MnII centers of the Mn5 cluster exhibit antiferromagnetic interactions.
Keywords: Calixarenes; Manganese; Magnetic property; Crystal growth; Solvothermal synthesis;

Synthesis and characterization of bisphenol sodium complexes: An efficient catalyst for the ring-opening polymerization of l-lactide by Xianrui Xu; Xiaobo Pan; Sifu Tang; Xiaoxia Lv; Liangjun Li; Jincai Wu; Xuebo Zhao (89-93).
Two sodium complexes, [(μ 3-MDBP)Na2(THF)2]2[(μ 3-OCH2CH2OCH3)Na]2 (1) and [(μ 1-MDBP)Na(μ 2-H2O)(THF)]2(THF)2 (2) have been synthesized and structurally characterized. Experimental results show that complex 1 initiates efficiently the ring opening polymerization of l-lactide in a controlled fashion, yielding polymers with narrow polydispersity indexes in a wide range of monomer-to-initiator ratios.Two new sodium complexes, [(μ3-MDBP)Na2(THF)2]2[(μ3-OCH2CH2OCH3)Na]2 (1) and [(μ1-MDBPH)Na(μ2-H2O)(THF)]2(THF)2 (2) were synthesized by reaction of sodium or sodium hydroxide with the bisphenol ligand of 6,6′-methylenebis(2,4-ditert-butylphenol) (MDBP-H2). And experimental results show that complex 1 is an excellent initiator for the ring-opening polymerization of l-lactide.Display Omitted► Two binuclear and hexanuclear sodium complexes of bisphenol have been synthesized. ▶ The catalytic activities of complex 1 for ROP of lactides have been investigated. ▶ The positive experimental results showed that complex 1 was an excellent catalyst.
Keywords: Sodium complexes; Catalyst; Ring opening polymerization; Polydispersity indexes;

Two new metal-organic frameworks, [Zn2(FA)2(bix)2]n  · 3nH2O (1) and [Zn(FA)(bib)]n (2), (H2FA = fumaric acid, bix = 4,4′-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazolyl)butane), have been synthesized by combining the fumaric acid and flexible imidazole-based ligands with Zn(II) salts under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 is a 4-fold interpenetrated unc topological net, and 2 is a 5-fold interpenetrated dia topological net. Moreover, the luminescent properties of the two compounds were also investigated in the solid state at room temperature.Two new luminescent metal-organic frameworks, [Zn2(FA)2(bix)2]n  · 3nH2O (1) and [Zn(FA)2(bib)2]n (2), (FA = fumaric acid, bix = 4,4′-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazolyl)butane), with distinct topological frameworks were successfully obtained through altering auxiliary ligand.Display Omitted► Two compounds obtained through altering auxiliary ligand. ► Two luminescent compounds with distinct topology. ► They exhibit intense ligand-centered luminescence.
Keywords: Hydrothermal synthesis; Metal-organic framework; Interpenetration; Topology;

Synthesis, characterization, photochemical properties and cytotoxicity of the novel porphyrazine functionalized with nitroimidazolylbutylsulfanyl groups by Sebastian Lijewski; Jaroslaw Piskorz; Malgorzata Kucinska; Marcin Wierzchowski; Katarzyna Czerniak; Hanna Billert; Marek Murias; Jadwiga Mielcarek; Tomasz Goslinski (97-100).
A novel porphyrazine analog possessing nitroimidazolylbutylsulfanyl groups was synthesized and characterized using UV–Vis, IR, MS MALDI and various NMR techniques. In addition, a computational model following the Density Functional Theory method (DFT) was applied to analyze the FT IR spectrum. Potential photosensitizing activity of the novel porphyrazine was evaluated by measuring its ability to generate singlet oxygen (Φ Δ), which was found to reach the value of 0.045 in DMF, and 0.035 in DMSO. A lower value of singlet oxygen generation in DMSO may result from the increased tendency to aggregate, which was studied in the UV–Vis and it was found to be stronger in DMSO than in DMF solutions. The investigation indicated no release of nitric oxide (NO) from porphyrazine functionalized with nitroimidazolylbutylsulfanyl groups. In vitro studies of the new compound were carried out to investigate photosensitizer-induced photocytotoxicity on two prostate human cancer cell lines, LNCaP, PC3, and one melanoma derived cell line, MeWo.A novel porphyrazine analogue possessing nitroimidazolylbutylsulfanyl groups was synthesized and characterized using UV–Vis, IR, MS MALDI, NMR techniques and the DFT method. Photosensitizing activity was evaluated by measuring its ability to generate singlet oxygen (Φ Δ) and photosensitizer-induced photocytotoxicity on two prostate human cancer and one melanoma derived cell lines.Display Omitted► Porphyrazine possessing nitroimidazolylbutylsulfanyl groups was synthesized. ► Potential photosensitizing activity of the novel porphyrazine was evaluated. ► Photocytotoxicity induced by porphyrazine was investigated in vitro.
Keywords: Nitroimidazole; Porphyrazine; Linstead macrocyclization; Singlet oxygen generation; Carcinoma;

A novel oxidorhenium(V) complex with 2-(aminomethyl)benzimidazole has been synthesized and spectroscopically characterised. The crystal structures of its solvates [Re2O3Cl4(ambi)2]·CH3COCH3 and [Re2O3Cl4(ambi)2]·CH3CN have been determined. The experimental studies have been accompanied computationally by the density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The information about the Re―O bond characteristics of [Re2O3Cl4(ambi)2] was obtained by NBO analysis.A dinuclear oxidorhenium(V) complex incorporating 2-(aminomethyl)benzimidazole has been synthesized and characterised by spectroscopic methods. Depending on the recrystallization conditions, two types of crystals [Re2O3Cl4(ambi)2]·CH3COCH3 and [Re2O3Cl4(ambi)2]·CH3CN were isolated and both were structurally characterised by X-ray diffraction analyses. Its electronic structure and spectrum were studied by DFT methods.Display Omitted► New dinuclear Re(V) complex with a linear Re2O3 4+ core was synthesized. ► The crystal structures of its solvates were characterized by single crystal X-ray diffraction. ► The complex was characterized by ESI-MS, FT-IR, 1H NMR, and UV-Vis spectroscopy. ► Its structural and electronic properties were also studied by DFT methods. ► Its electronic spectrum have been reproduced by the TD-B3LYP/LANL2DZ method.
Keywords: Oxidorhenium(V) complexes; X-ray structure; UV–vis spectrum; DFT and TDDFT calculations;

A novel metal–organic framework, namely [Cd3(NTC)2(bimh)3⋅ 2H2O]⋅ H2O (1) (H3NTC = 5-nitrobenzene-1,2,3-tricarboxylic acid, bimh = 1,6-bis(imidazol-1-yl)-hexane), has been hydrothermally synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction. Compound 1 presents a three dimensional 3-fold interpenetrated (3,4)-connected framework with the topology symbol of (4 × 6 × 8)(4 × 62  × 83)2(64  × 8 × 10). In addition, the fluorescent property and thermal stability of 1 were discussed.A novel coordination polymer features an interesting 3-fold interpenetrated 3D structure and can be described as trinodal (3,4)-connected framework. The fluorescent property of compound 1 indicates that it may be good candidates for blue-light emitting material.Display Omitted► A new 3D coordination polymer with three-fold interpenetration is observed. ► It presents a (3, 4)-connected framework. ► Flexible bis(imidazole) and rigid 5-nitrobenzene-1,2,3-tricarboxylic co-ligands. ► The Fluorescence property and thermal stability were discussed.
Keywords: Metal–organic framework; 5-nitrobenzene-1,2,3-tricarboxylic acid; Topology; Fluorescent;

Solvent induced structural variation in magnesium carboxylate frameworks by Tingzhi Liu; Daibing Luo; Dingguo Xu; Hongmei Zeng; Zhien Lin (110-113).
Four magnesium-based coordination polymers, formulated as Mg(ndc)(dmi) (1), Hdmu⋅Mg2(ndc)2(OH)(dmu)4 (2), Mg(ndc)(dma) (3), and Mg(ndc)(nmp)·0.5H2O (4), were prepared in an effort to investigate the effect of organic solvents on the framework structures. Compounds 1 and 2 have layered structures with a sql topology. Compounds 3 and 4 have three-dimensional structures with 4-connected pts and lvt-b topologies, respectively. The solvents exhibit multiple functions in the solvothermal reactions as a terminal ligand, bridging ligand, and charge-balancing agent.Four magnesium-based coordination polymers have been synthesized in an effort to investigate the effect of organic solvents on the framework structures. These compounds display three types of 4-connected topologies, termed sql, pts and lvt-b, respectively.Display Omitted► Four coordination polymers have been prepared under solvothermal conditions. ► Paddle-wheel Mg2(CO2)4 unit has been observed for the first time. ► These compounds display 4-connected frameworks with sql, pts and lvt-b topologies, respectively.
Keywords: Solvothermal synthesis; Coordination polymer; Magnesium; Carboxylate; Topology;

Direct oxidation of alcohols to carboxylic acids over ruthenium hydride catalyst with diphenyl sulfoxide oxidant by Behjat Barati; Majid Moghadam; Abbas Rahmati; Valiollah Mirkhani; Shahram Tangestaninejad; Iraj Mohammadpoor-Baltork (114-117).
In the present work, a new method for the synthesis of carboxylic acids over ruthenium hydride catalyst is reported. Direct oxidation of alcohols to their corresponding carboxylic acids with diphenyl sulfoxide oxidant over RuHCl(CO)(PPh3)3 catalyst was investigated. Mild reaction conditions, short reaction times and excellent yields make this method as an appealing way for preparation of carboxylic acids.A new and efficient method for the direct oxidation of alcohols to their corresponding carboxylic acids with diphenyl sulfoxide as oxidant in the presence of catalytic amounts of RuHCl(CO)(PPh3)3 is reported. Mild reaction conditions, short reaction times and excellent yields are the advantages of the present work.Display Omitted► The RuHCl(CO)(PPh3)3 was used as catalyst. ► Alcohols were directly oxidized to carboxylic acids. ► Diphenyl sulfoxide was used as oxidant.
Keywords: Ruthenium hydride complex; Carboxylic acid; Diphenyl sulfoxide; Direct oxidation;

Zinc and thiocyanate-mediated oxazolidine ring formation in a trinuclear zinc(II) complex: Synthesis, structure, and properties by Hai-Hua Li; Zhong-Lu You; Cheng-Lu Zhang; Mei Yang; Li-Na Gao; Lu Wang (118-122).
A novel trinuclear zinc(II) complex, [Zn3L2(NCS)2], where L is the deprotonated form of 2-(3-(2-(2-hydroxy-3-methoxybenzylideneamino)ethyl)oxazolidin-2-yl)-6-methoxyphenol (H2L), has been unexpectedly prepared from the reaction of Schiff base ligand 2-((2-(2-hydroxyethylamino)ethylimino)methyl)-6-methoxyphenol (HL′) with 3-methoxysalicylaldehyde, ammonium thiocyanate, and zinc nitrate in methanol. The complex has been characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction studies. It is interesting that the Schiff base ligand HL′ used to prepare the complex was transferred to a novel ligand H2L, bearing newly formed oxazolidine ring. Zinc ion and thiocyanate anion may be the essential factors for the cyclorization. Thermal stability and fluorescent property of the complex were also studied.A novel trinuclear zinc(II) complex has been unexpectedly prepared from the reaction of Schiff base ligand 2-((2-(2-hydroxyethylamino)ethylimino)methyl)-6-methoxyphenol with 3-methoxysalicylaldehyde, ammonium thiocyanate, and zinc nitrate in methanol. Zinc ion and thiocyanate anions may be the essential factors for the cyclorization between the ligands.Display Omitted► A new trinuclear zinc complex with Schiff base ligands was prepared. ► The complex has been characterized by single crystal X-ray diffraction. ► Zinc ion and thiocyanate anions may be the essential factors for the cyclorization. ► The probable mechanism was presented. ► Thermal stability and fluorescence of the complex were studied.
Keywords: Schiff base; Zinc; Trinuclear complex; Cyclorization;

A novel and improved room temperature synthesis of the monohydride catalyst trans-[RuCl(H)(dppe)2] complex (1, dppe (1,2-bis(diphenylphosphino)ethane) = Ph2PCH2CH2PPh2) proceeds through oxidation of methanol (the solvent) by the pentacoordinated cis-[RuCl(dppe)2][PF6] complex and t-BuOK as the base is described. Compound 1 was fully characterized by NMR (1H, 13C, 31P), ESI-MS(TOF +), FTIR and elemental analysis. The X-ray structure of 1 was reported for the first time and unambiguously confirms the trans-configuration of the complex.A new and easy way to synthesize the trans-[RuCl(H)(dppe)2], (1) in high-yield was presented and its X-ray structure was reported for the first time.Display Omitted► A faster way to access the catalyst trans-[RuCl(H)(dppe)2](1) is presented. ► Compound 1 X-ray structure is presented for the first time. ► The synthesis of 1 is a cost effective pathway for the preparation of derivatives. ► Room temp. synthesis of 1 is important in domains beyond catalysis and materials.
Keywords: Ruthenium; Hydrogenation; Homogeneous catalysis; Hydrides; Synthetic methods; X-ray crystal structure;

Ultrafast microwave-enhanced ionothermal synthesis of luminescent crystalline polyimide nanosheets for highly selective sensing of chromium ions by Juan-Ding Xiao; Ling-Guang Qiu; Yu-Peng Yuan; Xia Jiang; An-Jian Xie; Yu-Hua Shen (128-130).
Highly luminescent crystalline polyimide (PI) nanosheets in high yields (up to 95%) were facilely prepared through reaction between melamine and pyromellitic dianhydride via a microwave-enhanced high temperature ionothermal method within only a few minutes (~ 3 min). The as-synthesized luminescent crystalline PI nanosheets have been investigated as sensors for luminescence sensing investigations toward a series of metal ion solutions. Remarkably, such luminescent crystalline PI nanosheets exhibited highly sensitive and selective sensing of chromium ions in aqueous solution, without the interference of other metal ions, such as potassium, calcium, cadmium, plumbum, manganese, mercury, magnesium, cobalt, copper, and zinc.We present here ultrafast synthesis of highly luminescent crystalline polyimide (PI) nanosheets prepared through reaction between melamine and pyromellitic dianhydride by using a microwave-enhanced high temperature ionothermal method. Significantly, the as-prepared PI nanosheets exhibit highly selective sensing of Cr3 +, without the interference from other metal ions, such as K+, Ca2 +, Cd2 +, Pb2 +, Mn2 +, Hg2 +, Mg2 +, Co2 +, Cu2 +, Zn2 +, in aqueous solutions.Display Omitted► Ultrafast synthesis of luminescent crystalline polyimide (PI) nanosheets ► Sensing of chromium ion (Cr3 +) by PI nanosheets ► Highly selective sensing of Cr3 + without the interference from other metal ions.
Keywords: Microwave-assisted synthesis; Rapid synthesis; Nanocrystalline materials; Luminescence; Sensors; Chromium ions;

An unusual coordination compound, [Cu4(dmpz)2(mi)2H3PMoVI 8MoV 4O40]·6H2O (dmpz = 2,3-dimethylphenazine, mi = 2-methyl-1H-imidazole) (1), has been hydrothermally synthesized and characterized by elemental analysis, IR, XPS and single crystal X-ray diffraction. Compound 1 consists of dmpz and mi organic ligands, CuI cations and [H3PMoVI 8MoV 4O40]4 − polyoxoanions. Interestingly, the dmpz organic ligands are from in situ reaction of 1,2-diaminobenzene (dab) and 1,2-benzenedicarboxylic acid (bdc).The dmpz ligands are from in situ synthesis of dab and bdc under the hydrothermal reaction conditions.Display Omitted► There are two kinds of ligands in the complex. ► The dmpz ligands are from in situ synthesis of dab and bdc. ► There are π–π packing interactions of organic ligands in compound 1.
Keywords: In situ synthesis; Keggin; Hydrothermal synthesis;

The flexibility of binding modes of the supersilyl thiolate ligand SSitBu3 by Frank Meyer-Wegner; Michael Bolte; Hans-Wolfram Lerner (134-137).
The synthesis and structural characterization of [Zn(SSitBu3)2]2 are described. The degradation of sulfur with [Zn(SitBu3)2] in tetrahydrofuran yielded the supersilyl thiolate complex [Zn(SSitBu3)2]2. X-ray quality crystals of [Zn(SSitBu3)2]2 were grown from a benzene solution at ambient temperature (monoclinic, C2/c). The trigonal-planar coordinate zinc atoms in [Zn(SSitBu3)2]2 are surrounded by one terminal and two bridging thiolate ligands. The bonds between the Zn and S atoms of the terminal ligands are significantly shorter than those between the Zn and S atoms of the bridging ligands.The degradation of sulfur with [Zn(SitBu3)2] in tetrahydrofuran yielded the supersilyl thiolate complex [Zn(SSitBu3)2]2. The crystal structure of [Zn(SSitBu3)2]2 displays trigonal-planar coordinate zinc atoms which are surrounded by one terminal and two bridging thiolate ligands.Display Omitted► Treatment of S8 with [Zn(SitBu3)2] yields [Zn(SSitBu3)2]2. ► Supersilyl thiolate ligands in [Zn(SSitBu3)2]2 reveal two different binding modes. ► The structure of [Zn(SSitBu3)2] displays terminal and bridging thiolate ligands.
Keywords: Supersilyl; Thiolate; Chalcogenolate; X-ray structure analysis;

Fluorescent metallopolymers with Zn(II) in a Schiff base/phenoxide coordination environment by Ugo Caruso; Barbara Panunzi; Antonio Roviello; Angela Tuzi (138-140).
An iminic derivative of 2-amino-6-methylbenzothiazole, able to generate on deprotonation a mononegative ligand moiety and the corresponding tetracoordinate zinc (II) complex are reported. The complex is centrosymmetrical and difunctionalized with two OH groups that have been used for omo- and co-polymerisation with a diisocyanate to form four polyurethanes with various zinc content.The thermodynamic and optical properties of the complex and of the polymers were investigated by calorimetry, polarizing microscopy and X-ray diffraction technique. In particular, the fluorescence properties of the complex and of the polymers were explored.Display Omitted► Preparation and properties of tetracoordinate zinc (II) complex OH difunctionalized. ► Preparation and the properties of omo and co polyurethanes with a diisocyanate. ► Examination of fluorescence properties of the complex and of the polymers. ► Measurements of solid state quantum yield on the most promising polymer.
Keywords: Zn(II) complex; Metallopolymer; Fluorescence;

Synthesis, structure, and catalytic activity of a new chiral NHC–iridium(III) complex by Liang Chen; Yuqiao Liu; Guohua Hou; Haibin Song; Guofu Zi (141-144).
The new chiral NHC–iridium complex 3 has been prepared in CH3CN from the reaction between [Ir(COD)Cl]2, NaOAc, KI, and dibenzimidazolium salt 2 which is derived from (S)-2,2′-diamino-6,6′-dimethyl-1,1′-biphenyl. Complex 3 has been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analysis. It has a distorted-octahedral IrC2N2IH core structure, and shows good catalytic activity for the asymmetric hydrosilylation of arylmethyl ketones, leading to 1-arylethanol with moderate ee values.A new NHC–iridium complex has been prepared and structurally characterized. It shows good catalytic activity for the asymmetric hydrosilylation of arylmethyl ketones.Display Omitted► A new chiral NHC–iridium complex has been prepared and structurally characterized. ► It has a distorted-octahedral IrC2N2IH core structure. ► It is an active catalyst for the asymmetric hydrosilylation of arylmethyl ketones.
Keywords: Carbene complex; Iridium; Biphenyl ligand; Asymmetric hydrosilylation;

A novel lithium aggregate complex [(μ2-/μ3-EDBP)2(OCHCH2)Li5(THF)4] (1) has been synthesized by the reaction of 2,2′-ethylidenebis(4,6-di-tert-butyl-phenol) (EDBP-H2) with 2.5 eq n BuLi in tetrahydrofuran with high yield. The structure of complex 1 is determined by 1H-NMR and X-ray crystallography. Complex 1 can initiate the living ring-opening polymerization of ε-caprolactone and l-lactide yielding polymers with narrow molecular weight distributions, and moreover to prepare the PCL-b-PLA block copolymer.A novel lithium aggregate complex containing bis(phenolate) and enolate mixed ligands was synthesized and characterized by X-ray crystallography. The complex is an efficient initiator for the living ring-opening polymerization of ε-caprolactone as well as l-lactide.Display Omitted► Synthesis of lithium aggregate with bis(phenolate) and enolate mixed ligands. ► X-ray diffractions studies on this complex. ► Living ROP of ε-caprolactone and L-lactide initiated by this complex.
Keywords: Lithium complexes; Enolate; Ligands; Polymerization; Cyclic esters;

Temperature-dependent urothermal synthesis of two distinct La(III)-naphthalenedicarboxylate frameworks by Duan-Chuan Hou; Gui-Yuan Jiang; Zhen Zhao; Jian Zhang (148-150).
Two distinct La(III)-naphthalenedicarboxylate frameworks, namely La2(NDC)3(e-urea)3 (1; H2NDC = 2,6-naphthalenedicarboxylic acid; e-urea = ethyleneurea) and La(NDC)1.5(e-urea) (2), have been successfully synthesized through urothermal synthesis under different temperatures. Single-crystal X-ray structural analysis revealed that both compounds 1 and 2 feature three-dimensional (3D) structures with open channels occupied by the coordinated e-urea molecules. Interestingly, e-urea molecules and NDC ligands adopt distinct coordination modes in two structures. Furthermore, thermal analyses of 1 and 2 were also investigated.Urothermal synthesis of two distinct La(III)-naphthalenedicarboxylate frameworks under different temperatures are presented.Display Omitted► Urothermal synthesis of two different La(III)-organic frameworks ► The first example of temperature-dependent urothermal synthesis ► Two three-dimensional structures with open channels
Keywords: Temperature-dependent; Crystal structure; Urothermal synthesis; Hydrogen bond;

The triethylbenzylammonium perchlorate, C13H22N+·ClO4 was synthesized and separated as block colorless crystals. DSC measurement detected that this compound undergoes a reversible phase transition at ca. 196 K with a hysteresis of 18 K width. Dielectric measurements also confirm the transition. The crystal structures determined at 93(2) K (a  = 12.114(4)Å, b  = 14.320(5)Å, c  = 16.418(6)Å, V  = 2848.0(17)Å3, Z  = 8) and 291(2) K (a  = 8.3891(17)Å, b  = 12.300(1)Å, c  = 14.513(1)Å, V  = 1497.5(3) Å3, Z  = 4) show that the phase transition is a type of isosymmetric change with the space group of Pbca (No. 61) in the low-temperature phase (LTP) to the space group of Pbcm (No. 57) in the room-temperature phase (RTP). The distinct difference between the LTP and the RTP structure is the different orientation for the anions and the H-bond interactions between the perchlorate anions and triethylbenzylammonium cations. Hydrogen bond interactions may play a role in the phase transition as shown by the changes in the hydrogen bonding pattern as the temperature decreased. The order–disorder type transition of the anions is probably the driving force of the phase transition.The temperature-induced isosymmetric reversible structural phase transition from a room temperature paraelectric phase (Pbcm) to a low temperature one (Pbca) in triethylbenzylammonium perchlorate was evidenced by DSC, dielectric measurements and variable-temperature structural analysis, Order-disorder transition of the anions is probably the driving force to the phase transition.Display Omitted► An isosymmetric reversible phase transition compound is synthesized. ► DSC, dielectric and structural analyses confirm the phase transition at 196 K. ► The order-disorder transition of the anions is probably the driving force.
Keywords: Phase transition; Order–disorder; Differential scanning calorimetry; Dielectric; Variable–temperature X-ray;

A dimeric aluminum complex bridged by alkoxide with pendant aniline group was synthesized and characterized. X-ray analysis revealed that the two four-coordinate aluminum centers possess a distorted tetrahedral geometry with C2h symmetry. The compound was used as an effective catalyst for the controlled ring opening polymerization of L-lactide, as shown by the linearity of the number average of the molecular weight of polylactides versus conversion, as well as narrow Mw/Mn values.Short Synopsis: A dimeric aluminum complex which has a distorted tetrahedral geometry with C2h symmetry around two four-coordinate aluminum centers has synthesized and used as a catalyst for controlled/living ring opening polymerization of L-lactide at 70 and 130 °C.Display Omitted► 2-Methyl-1-(phenylamino)propan-2-ol (PhNHCH2CMe2OH) was used as a ligand. ► AlMe3 was used as a metal precursor. ► C2h symmetric aluminum complex with Al2O2 four-membered ring was prepared. ► Aluminum catalyst was used for controlled ring opening polymerization of lactide.
Keywords: Aluminum; 2-Methyl-1-(phenylamino)propan-2-ol; Dimeric; Polylactide; X-ray crystal structure;

Template synthesis, structure and electropolymerization of the 2-thiopheneboron-capped cobalt(II) clathrochelates by Alexander S. Belov; Alexander V. Dolganov; Valentin V. Novikov; Anna V. Vologzhanina; Matvey V. Fedin; Evgenii V. Kuznetsov; Yurii N. Bubnov; Yan Z. Voloshin (160-164).
2-thiopheneboron-capped macrobicyclic cobalt(II) tris-dioximates were synthesized by direct template condensation of the corresponding α-dioxime with 2-thiopheneboronic acid on a cobalt(II) ion as a matrix; they were characterized by spectral methods and X-ray crystallography. Further electropolymerization of their redox-active apical substituents afforded the polymeric clathrochelate electrocatalysts for hydrogen production from H+ ions.2-thiopheneboron-capped macrobicyclic cobalt(II) tris-dioximates were synthesized by direct template condensation of the corresponding α-dioxime with 2-thiopheneboronic acid on a cobalt(II) ion as a matrix and characterized by spectral methods and X-ray crystallography. Further electropolymerization of their redox-active apical substituents afforded the polymeric clathrochelate electrocatalysts for hydrogen production from H+ ions.Display Omitted► Thiopheneboron-capped clathrochelate coablt(II) tris-dioximates were obtained. ► Electropolymerization of their apical substituents afforded polymeric clathrochelates. ► The structures of the cobalt(II) clathrochelates undergo Jahn-Teller distortion. ► Hexachlorine-containing Co(II) clathrochelate undergo spin transition 1/2 ↔ 3/2 ► Co(II) clathrochelates and the electropolymers are electrocatalysts for H2 production.
Keywords: Macrocyclic compounds; Clathrochelates; Cobalt complexes; Electropolymerization; Hydrogen production;

Lead–vitamin complex [Pb(C19H15N7O6)]·4H2O and its application in bioimaging by Fangfang Zhao; Hengchao Zhang; Hailiang Hu; Guangju Zhang; Kai Yang; Ruihua Liu; Haitao Li; Yang Liu; Zhuang Liu; Zhenhui Kang (165-168).
A new lead–vitamin complex [Pb(C19H15N7O6)]·4H2O with strong fluorescence was successfully used as biological fluorescent probe for cellular bioimaging.Lead–vitamin complex [Pb(C19H15N7O6)]·4H2O with strong fluorescence was successfully used as biological fluorescent probe for cellular bioimaging.Display Omitted► New water-soluble metal–vitamin compound ► Significantly enhanced fluorescence intensity ► Good cellular uptake of the title compound
Keywords: Lead–vitamin complex; Fluorescence; Bioimaging;

New silver(I) coordination polymer containing a rare inorganic graphite-like [AgS]n layer by Xin-Ping Kang; Ying-Shuang Hu; Li-Hua Zhu; Zhe An (169-171).
A new metal-organic coordination polymer, namely [Ag2(H2trzS)2Cl2]n (1, H2trzS = 1H-1, 2, 4,-triazole-3-thiol), has been successfully synthesized under solvothermal conditions and characterized by elemental analysis, FT-IR spectra and powder X-ray diffraction (PXRD). Single crystal X-ray diffraction analysis reveals that 1 features a two-dimensional (2D) layer structure with a rare inorganic graphite-like [AgS]n layer. Optical diffuse reflectance study reveals an optical band gap of 3.83 ev, making it a wide band gap semiconductor. The densities of states (DOS) calculations reveal that the luminescent emission of 1 originates from the intraligand-charge-transfer.Presented here is a new Ag(I) coordination polymer, namely [Ag2(H2trzS)2Cl2]n (1, H2trzS = 1H-1, 2, 4,-triazole-3-thiol), which contains a rare inorganic graphite-like [AgS]n layer. Optical diffuse reflectance study reveals an optical band gap of 3.83 ev, making it a wide band gap semiconductor.Display Omitted► A new luminescent Ag(I) coordination was successfully synthesized. ► Compound 1 features a rare inorganic graphite-like [AgS]n layer. ► Optical diffuse reflectance study reveals an optical band gap of 3.44 ev.
Keywords: Solvothermal synthesis; Coordination polymer; 1H-1, 2, 4,-triazole-3-thiol; Luminescence;

2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)-pyridine: Structures of An(III) and Ln(III) 1:3 complexes and selectivity by Nidhu L. Banik; Melissa A. Denecke; Andreas Geist; Giuseppe Modolo; Petra J. Panak; Jörg Rothe (172-174).
In continuation of previous studies, 1:3 complexes between Sm(III), Dy(III), Ho(III) or Tm(III) and 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)-pyridine (n-Pr-BTP) are prepared and their coordination structure in solution characterised by means of extended X-ray absorption fine structure (EXAFS). In addition, distribution ratios D M(III) for the extraction of Np(III), Cf(III) and Pm(III) are determined and compared to those for Pu(III), Am(III), Cm(III) and the other Ln(III).While Ln(III)–N bond lengths follow the lanthanide contraction in lanthanide(III)–BTP 1:3 complexes, An(III)–N bond lengths in the respective actinide(III) complexes are essentially constant, as shown by EXAFS studies performed in solution. Whether this difference plays a role in BTPs observed selectivity for actinides(III) over lanthanides(III) remains to be answered.Display Omitted► Extraction of actinides(III) and lanthanides(III) with BTP was studied. ► Solution structures of [M(BTP)3]3 + complexes were determined by EXAFS. ► Bond lengths in the [Ln(BTP)3]3 + complexes follow the Ln ionic radii. ► Bond lengths in the [An(BTP)3]3 + complexes are independent of the An ionic radii.
Keywords: Actinides(III); Lanthanides; BTP; N-donor ligands; EXAFS; Selectivity;

Chromogenic mercury ions recognition of a new ruthenium(II) complex with cyclometalated 2-(2-thienyl)pyridine in CH3CN-aqueous system by Xiang-Hong Li; Zhengjian Shi; Longlong Wang; Xinjian Cheng; Chunya Li; Aiqing Zhang (175-178).
A new cyclometalated complex [Ru(II)(deeb)2(thpy)]PF6 (1) was synthesized using 4,4′-diethylester-2,2′-bipyridine (deeb) and 2-(2-thienyl)pyridine (thpy) as ligands. Its maximum MLCT absorption is about 575 nm, extending beyond 750 nm. When Hg2 + was added to the CH3CN-aqueous solution of 1, a remarkable color change from dark-red to yellow with a blue-shift of 120 nm occurred, which indicated that the as-prepared complex 1 can serve as a sensitive “naked-eye” indicator for Hg2 +.A new cyclometalated complex [Ru(II)(deeb)2(thpy)]PF6 (1) as chemo-sensor was synthesized using 4,4′-diethylester-2,2′-bipyridine (deeb) and 2-(2-thienyl)pyridine (thpy) as ligands. Its maximum MLCT absorption is about 575 nm. When Hg2 + was added to the CH3CN-aqueous solution of 1, a remarkable color change from dark-red to yellow with a blue-shift of 120 nm occurred, which indicated that 1 can serve as a sensitive “naked-eye” indicator for Hg2 +.Display Omitted► A cyclometalated ruthenium complex with 2-(2-thienyl)pyridine was synthesized. ► Its maximum MLCT absorption is about 575 nm. ► It can serve as a sensitive naked-eye indicator for Hg2 + with a blue-shift of 120 nm.
Keywords: Cyclometalated ruthenium complex; Mercury ions; MLCT absorptions; Thiophene; Chemo-sensor;

Synthesis, structure and reactions of triply selenolate-bridged diiron complex [Cp*Fe(μ-SeMe)3FeCp*] by Jinfeng Zhao; Lei Wang; Yuhan Zhou; Yixin Zhang; Nan Zhang; Chunmei Jia; Fengshuo Hu; Yanhui Chen; Baomin Wang; Jingping Qu (179-182).
Two new iron–selenolate complexes [Cp*Fe(μ-SeMe)3FeCp*] (Cp* =  η 5-C5Me5) (1) and [Cp*Fe(μ-SeMe)3FeCp*][FeCl3] (2) were prepared by the oxidative addition reaction of MeSeSeMe with [Cp*FeCl]2 in 25% and 20% yields, respectively. In refluxing toluene, the methyl groups in the selenolate ligands of complex 1 were removed, affording a cubane cluster [Cp*4Fe4Se4] (3) in 50% yield. Complex 1 was oxidized by HBF4 to give [Cp*Fe(μ-SeMe)3FeCp*][BF4] (4), and the reverse reduction reaction occurred in the presence of CoCp2.Presented here is the syntheses of [Cp*Fe(μ-SeMe)3FeCp*] and [Cp*Fe(μ-SeMe)3FeCp*][FeCl3] by the oxidative addition reaction of MeSeSeMe with [Cp*FeCl]2. The conversion of [Cp*Fe(μ-SeMe)3FeCp*] into [Cp*4Fe4Se4] and [Cp*Fe(μ-SeMe)3FeCp*]+ were also explored.Display Omitted► Four new selenolate-bridged multi-iron clusters with Cp* as ligand were prepared. ► [Cp*Fe(μ-SeMe)3FeCp*] was converted into a cubane-type complex in heating toluene. ► [Cp*Fe(μ-SeMe)3FeCp*] and [Cp*Fe(μ-SeMe)3FeCp*]+ are interconvertible.
Keywords: Iron–selenolate complex; Oxidative addition reaction; Cubane cluster; Crystal structures;

A novel 3D Co(II) complex [Co(Hhmt)(H2O)∙H2O] (1) (H3hmt = 3,5-bis (hydroxymethyl)-1,2,4-triazole) has been hydrothermally synthesized. X-ray single crystal diffraction experiment reveals that each Hhmt2 − ligand connects three Co(II) ions to form a 3D lvt topological framework with the (42  ∙ 84) point symbol, especially for the existence of a considerable 2D channel. The magnetic and electrochemical properties of 1 are also discussed.A novel 3D metal-organic framework with a considerable 2D channel and (42∙ 84) point symbol of lvt topology, [Co(Hhmt)(H2O)∙H2O] was synthesized, where the thermal stability, magnetic and electrochemical properties have also been described for the complex.Display Omitted► The construction of a novel MOFs with a considerable 2D channel. ► The reported complex is a 3D lvt topological framework. ► The magnetic and electrochemical properties.
Keywords: Co(II) complex; Topology; 3,5-Bis(hydroxymethyl)-1,2,4-triazole; Magnetic and electrochemical properties;

With the different carboxylate as pillars two novel manganese(II) complexes [Mn2 TzDC3 − (NIO) (H2O)2]·(H2O)3.5 (1) and [Mn2 TzDC3 −(IMA) (H2O)2]·(H2O)2 (2) (TzDC3 −  = 1,2,3-triazole-4,5-dicarboxylate, NIO = nicotinate N-oxide and IMA = imidazol-1-yl-acetate) were obtained. The ligands TzDC3 − bridged metal ions to form Kagomé layers, which were further pillared by NIO and IMA resulting in similar pillar-layer structure but distinct topology net in 1 and 2. Magnetic study indicated that antiferromagnetic interactions are in 1 and 2 with spin competition.1,2,3-triazole-4,5-dicarboxylate constructed Kagomé layer were pillared by rigid and flexible ligands resulting in two distinct topology net. Magnetic study indicated antiferromagnetic interactions with strong competition in two complexes.Display Omitted► Kagomé layers were constructed by 1,2,3-triazole-4,5-dicarboxylate. ► Kagomé layers are supported by rigid and flexible ligands with distinct topology. ► Antiferromagnetic interactions are conducted by the ligands in the two complexes.
Keywords: Layer-Pillar Structure; Rigid and flexible; Kagomé; Topology; Magnetism;

DNA binding, cytotoxicity and DNA cleavage promoted by gold(III) complexes by Mohan N. Patel; Bhupesh S. Bhatt; Promise A. Dosi (190-193).
Square planar Au(III) complexes of 2,2′-dipyridylamine (A1), di(2-pyridyl)ketone (A2), 2-(4-chlorophenyl)-1H-imidazo[4,5-f] [1,10] phenanthroline (A3) and 2-(4-bromophenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (A4) of type [Au(An)Cl2].Cl were synthesized and characterized using conductivity measurement, C,H,N elemental analysis, FT-IR, LC–MS, 1H and 13C NMR spectroscopy. The compounds manifested significant cytotoxic properties in vitro for brine shrimp lethality bioassay. The metal complexes were screened for series of DNA binding activity using UV–vis. absorption titration, hydrodynamic measurement and thermal DNA denaturation study. The nucleolytic activity was performed on plasmid pUC19 DNA. The Michaelis–Menten kinetic studies were performed to evaluate rate of enhancement in metal complexes mediated DNA cleavage over the noncatalyzed DNA cleavage.Square planar gold(III) complexes have been synthesized using neutral bidentate NN donor ligands. Their DNA interaction and cytotoxic properties have also been evaluated.Display Omitted► Synthesis and characterization of gold(III) complexes ► DNA interaction studies suggest complexes as a covalent binder. ► Brine shrimp lethality bioassay was performed to check the cytotoxicity of complexes. ► Evaluation of Michaelis–Menten kinetic parameters of DNA cleavage reaction
Keywords: Au(III) complexes; Covalent binding; Reaction kinetics;

Different coordination modes of dipyridyl ketimine ligands in cationic arene ruthenium complexes by Mathiyazhagan Ulaganatha Raja; Bruno Therrien; Georg Süss-Fink (194-196).
2,2′-Dipyridyl-N-arylimines L (L1  = 2,4,6-trimethyl(di-2-pyridylmethylene)aniline, L2  = 2,6-diisopropyl(di-2-pyridylmethylene)aniline) react with arene ruthenium dichloride dimer in methanol to give cationic arene ruthenium complexes of the general type [(arene)Ru(η2-N,N-L)Cl]+ (arene = C6H6, p-MeC6H4Pri). Two coordination modes of the chelating ligands N,N-L are observed. In the major isomer, the ketimine nitrogen atom and one of the two pyridine nitrogen atoms are coordinated to ruthenium, while in the minor isomer the two pyridine nitrogen atoms coordinate to the metal center. In the case of L1, the minor isomer of the p-cymene ruthenium chloro complex could be isolated as the tetrafluoroborate salt and characterized by single crystal X-ray analysis. The molecular structure of the major isomer was determined by X-ray crystallography in the case of the tetraphenylborate salt of the benzene ruthenium chloro derivative. In both structures, the ruthenium atom shows the expected pseudo-tetrahedral coordination geometry.The cationic complexes [(arene)Ru(η2-N,N-L)Cl]+ (arene = C6H6, p-MeC6H4Pri), accessible from [(arene)RuCl2]2 and 2,2′-dipyridyl-N-arylimines, exist in the form of two different coordination isomers.Display Omitted► Arene ruthenium complexes with 2,2’-dipyridyl-N-arylimine ligands were prepared. ► These complexes occur in the form of two coordination isomers. ► In the major isomer, a pyridine nitrogen and a ketimine nitrogen are coordinated. ► In the major isomer, the two pyridine nitrogen atoms are coordinated. ► The molecular structures of both isomers were confirmed by X-ray crystallography.
Keywords: Ruthenium; Arene; 2,2′-Dipyridyl imines; Coordination isomerism; Structure;

A new supramolecular assembly composed of decatungstate polyanion and Cu/O/W heterometallic cluster by Pan-Pan Shen; Ying-Nan Chi; Zheng-Guo Lin; Chang-Wen Hu (197-200).
A new supramolecular assembly of [(CuL)2(WO4)2{CuL(H2O)}2][W10O32] · 8H2O (1) (L = 4′-(2-pyridyl)-2,2′:6′,2′-terpyridine) containing a decatungstate polyanion and a novel cationic Cu/O/W heterometallic cluster was successfully synthesized and characterized by single crystal X-ray diffraction and IR. The tungsten atoms adopt different coordination geometry in anion and cation, octahedral geometry (WO6) in decatungstate cluster and rare tetrahedral geometry (WO4) in cation cluster. During the hydrothermal process, the decomposition and reassembly based on [W6O19]2 − lead to the formation of [W10O32]4 − and Cu/O/W heterometallic cluster.A new supramolecular assembly of [(CuL)2(WO4)2{CuL(H2O)}2] [W10O32] · 8H2O (1) (L = 4′-(2-pyridyl)-2,2′:6′,2′-terpyridine) was successfully synthesized, which is composed of a decatungstate polyanion and a novel cationic Cu/O/W heterometallic cluster.Display Omitted► A new compound 1 contains a [W10O32]4– and Cu/O/W heterometallic clusters. ► The W atoms adopt two coordination geometries in anion and cation clusters. ► The formation of 1 verifies the transformation from [W6O19]2– to [W10O32]4–.
Keywords: Isopolyoxotungstate transformation; Heterometallic cluster; Supramolecular assembly; In situ reaction;

Synthesis, structure, photochromic and fluorescent imaging properties of a 3D cadmium(II) complex [Cd2(AT)2(H2O)4]·H2O (AT = 5,5′-azotetrazolate) by Yan-Xuan Qiu; Wen-Bin Chen; Xue-Mei Lin; Meng Yang; Hua Yan; Fei-Xian Gao; Xiao-Jiang Ruan; Zhen-Jie Ou Yang; Wen Dong (201-204).
A 5,5′-azotetrazolate based Cd2 + complex of [Cd2(trans-AT)2(H2O)4]·H2O (1) has been synthesized and characterized by single crystal X-ray diffraction analysis. In 1, each Cd2 + ion coordinates to six N atoms from four AT2 − anions and two water molecules to form a dicapped trigonal prismatic coordination environment. Each coplanar AT2 − anion acts as a novel bis-bridging-chelating mode with six N atoms linking four different Cd2 + ions to form a 3D structure. The aqueous solution of 1 with the concentration of 7.5 × 10− 5  mol·L− 1 shows photochromism. The solid photoluminescence of 1 under UV-light or laser irradiation and the fluorescent imaging of the onion cell using 1 as imaging agent were also reported.A 3D cadmium(II) complex based on 5,5′-azotetrazolate (AT) ligand [Cd2(trans-AT)2(H2O)4]·H2O (1) has been synthesized and characterized and the photochromic and fluorescent imaging properties of 1 have been found and discussed.Display Omitted► A 3D Cd(II) complex based on 5,5′-azotetrazolate ligand has been synthesized. ► The aqueous solution of the complex shows photochromism. ► The solid of the complex can emit green photoluminescence. ► The complex can be employed as onion cell label.
Keywords: 5,5′-Azotetrazolate; Cadmium(II) complex; 3D structure; Photochromism; Fluorescent imaging;

Two-armed carbohydrozine ligand, H2L1 and its cobalt(III) and zinc(II) complexes (1 and 2) have been synthesized and characterized by single-crystal X-ray diffraction analysis. In the solid state, compound 1 has double-strand helicate structure involving ligand that twists to the central metal ions. Abundant π…π stacking interaction extended in the crystallographic bc plane. However, compound 2 has mesocate structure with a side-by-side arrangement of two ligands. The structure of zinc(II) compound 2 can be described as plane-symmetry one with symmetry plane perpendicular to the metal linker. The π…π stacking interaction existed in the crystallographic ac plane of compound 2. Weak intermolecular interactions play dominant roles in shaping the extended two-dimensional structures for all the molecules in the solid state. In solution, zinc(II) compound 2 exhibited strong ligand-based π*–π fluorescent emissions that can be tuned by the attached proton, a potential proton probe model.Metal-dependent assembly of helicate versus mesocate supramolecular structures was obtained. By virture of metal-induced deprotonation in the self-assembly, pH-responsive fluorescent property of Zn2 +-mesocate was reported.Display Omitted► Metal-dependent assembly of helicate versus mesocate supramolecular structures was obtained. ► Metal coordination induced deprotonation in the self-assembly. ► pH-responsive fluorescent property of Zn2 +-mesocate was reported.
Keywords: Helicate; Mesocate; Crystal structure; Fluorescence;

4,4-Bipyridinium ionic liquids exhibiting excellent solubility for metal salts: Potential solvents for electrodeposition by Atakilt Abebe; Shimelis Admassie; Ignacio J. Villar-Garcia; Yonas Chebude (210-212).
Newly synthesised 4,4-bipyridinium based ionic liquids exhibit good metal coordinating abilities and are able to dissolve metal salts at high concentrations. The ability to capture metal salts into the ionic liquid media facilitates the application of ionic liquids in many areas such as metal extraction or electrochemistry. The ionic liquid n-butyl-4,4-bipyridinium bis(trifluoromethyl)sulfonylamide ([C4Bipyr][Tf2N]) exhibits a large liquidus range and a wide electrochemical window. The successful electrodeposition of Cu (II) to Cu (0) from a solution of Cu(NO3)2 in [C4Bipyr][Tf2N] shows the potential of this new type of ionic liquids for electrodeposition.The newly synthesised n-butyl-4,4-bipyridinium bis(trifluoromethyl)sulfonylamide can coordinate to metal salts and hence dissolve them at high concentration. The cyclic voltammogram of the ionic liquid before and after the dissolution of Cu(NO3)2 shows that it is possible to use n-alkyl-4,4-bipyridinium ionic liquids as media for the electrodeposition of metals.Display Omitted► We have synthesized new 4,4-bipyridinium ionic liquids. ► 4,4-bipyridinium ionic liquids can coordinate to metal salts. ► Show high solubility for metal salts. ► 4,4-bipyridinium ionic liquids exhibit high thermal and electrochemical stability. ► The electrodeposition of cupper was successfully demonstrated in these ionic liquids.
Keywords: Ionic liquids; Metal salts; Bipyridinium; Bipyridine; Electrodeposition; Metal extraction;