Inorganic Chemistry Communications (v.38, #C)

Contents List (iii-xii).

Reaction of the chiral ligands (1S,4S)-2,5-bis(6-methylpyridyl)-diazabicyclo[2.2.1]heptane (L1 ) and (1S,4S)-2,5-bis(1-methyl-2-methylbenzimidazolyl)-diazabicyclo[2.2.1]heptane (L2 ) with CuCl2 results in the hydroxo-bridged dicopper complexes [(L1 )Cu2(μ-OH)(H2O)Cl3] (3), and [(L2 )Cu2(μ-OH)(H2O)Cl3] (4). Both chiral complexes were characterized spectroscopically, and 3 in the solid state by X-ray crystallography, confirming they are structurally related to their previously reported copper acetate analogues (1 and 2) due to their hydroxo-bridged bimetallic core. The achiral ligand analogues N,N′-bis(2-picolyl)piperazine (L3 ) and N,N′-bis(1-methyl-2-methylbenzimidazolyl)piperazine (L4 ) were employed to obtain the corresponding complexes with CuCl2, affording the chloro-bridged [(L3 )(CuCl)2(μ-Cl)2]n (5) and [(L4 )(CuCl)2(μ-Cl)2] (6), neither of which features a bridging hydroxo ligand; instead, complex 5 was structurally characterized as a coordination polymer. The acetate-derived complexes 1 and 2 are active in oxidative C–C coupling of 2,4-di-tert-butylphenol, while 3 and 4 have low activity; the achiral complexes 5 and 6, lacking a bridging hydroxo ligand, are inactive in this reaction.Piperazine-derived tetradentate ligands with pyridine and benzimidazole groups afford polymeric copper(II) chloride complexes; their chiral diazabicyclic analogues are active in catalytic oxidative phenol C–C coupling.Display Omitted
Keywords: Copper; Piperazine; Heterocycles; Chiral ligands; Oxidative coupling;

A new compound (NH4)2[Ni(H2O)5(NH3)]2[V10O28]·4H2O (1) containing a {V10O28}  6− anionic cluster and a novel complex cation, [Ni(H2O)5(NH3)]2 +, has been synthesized and fully characterized by single crystal X-ray crystallography, spectroscopy and thermogravimetric analysis. The presence of the ammonia ligand in the complex cation in 1 was established unambiguously by X-ray crystallography and variable temperature (200–400 °C) thermogravimetric analyses in combination with FTIR spectroscopic studies. The formation of the novel complex species {Ni(H2O)5(NH3)}2 + during the synthesis of 1 can be rationalized in terms of ligand substitution involving {Ni(H2O)6}2 +.A new compound (NH4)2[Ni(H2O)5(NH3)]2[V10O28]·4H2O containing a {V10O28}6 − anionic cluster and a novel complex cation, [Ni(H2O)5(NH3)]2 +, has been synthesized and fully characterized by single crystal X-ray crystallography, spectroscopy and thermogravimetric analysis.Display Omitted
Keywords: Decavanadate; Thermogravimetric analysis; Crystal structure; X-ray crystallography;

A new synthetic route for the preparation of metal tellurides by Václav Kubát; Zdeněk Losos; Zdeněk Trávníček; Josef Novosad (8-10).
A new method of synthesis for the formation of metal tellurides of the type MTe (M = Cd, Hg) is reported. The compounds were prepared by the reaction of cadmium carbonate (or mercury oxide, respectively) with tellurium and bis(diphenylphosphino)amine in toluene at 160 °C. The products were characterized by powder XRD and EDX analyses. The whole chemical process is discussed.Display Omitted
Keywords: Cadmium telluride; Mercury telluride; Synthesis; Bis(diphenylphosphino)amine;

A novel 3D metal-organic framework (Me2NH2)2[Cd3(H2-DHBDC)3(CH3COO)2(DMF)2](DMF)2 (H4-DHBDC = 2,5-dihydroxy-1,4-benzenedicarboxylic acid) with unusual [CdII 3O2(CO2)8] building blocks has been solvothermally synthesized. It features a typical pcu topology by reducing the [CdII 3O2(CO2)8] building blocks as the 6-connected nodes. The physical properties such as thermogravimetric analyses (TGA), IR, elemental analysis, powder X-ray diffraction (PXRD) and photoluminescence were investigated in detail.Presented here is a novel 3D metal-organic framework built from unusual [CdII 3O2(CO2)8] building blocks, showing 6-conntected pcu topology.Display Omitted
Keywords: Cadmium(II) complex; 2,5-dihydroxy-1,4-benzenedicarboxylic acid; Metal-organic framework; Photoluminescence;

Photo- and electroluminescence from deep-red- and near-infrared-phosphorescent tris-cyclometalated iridium(III) complexes bearing largely π-extended ligands by Shigeru Ikawa; Shigeyuki Yagi; Takeshi Maeda; Hiroyuki Nakazumi; Hideki Fujiwara; Shiro Koseki; Yoshiaki Sakurai (14-19).
Deep-red- and near-infrared-phosphorescent tris-cyclometalated iridium(III) complexes bearing largely π-extended cyclometalated (C^N) ligands were newly synthesized, and their photo- and electroluminescence properties were investigated. When 2-(benzo[b]furan-2-yl)quinoline and 2-(benzo[b]thiophen-2-yl)quinoline were employed as C^N ligands, deep-red photoluminescence was obtained (Ir-1a and Ir-1b; λPL in CH2Cl2, 647 and 652 nm, respectively). In the case of the isoquinoline analogues of Ir-1a and Ir-1b, emission maxima were further red-shifted, ranging from deep-red to near-infrared regions (Ir-2a and Ir-2b; λPL in CH2Cl2, 696 and 690 nm, respectively). Especially, Ir-2b showed an excellent photoluminescence quantum yield (Φ PL  = 0.15), and a polymer light-emitting diode doped with Ir-2b exhibited deep-red–near-infrared electroluminescence with a high external quantum efficiency (λEL  = 694 nm, η ext max  = 1.41%).We have developed novel tris-cyclometalated iridium(III) complexes emitting in the near-infrared (NIR) region. Especially, Ir-2b is very emissive for an NIR-phosphorescent material, the Φ PL of which is 0.15. A polymer light-emitting diode doped with Ir-2b has also exhibited NIR electroluminescence with a relatively high external quantum efficiency (η ext max  = 1.41%). The graphical abstract shows the electroluminescence spectrum of the PLED, along with the structure of Ir-2b.Display Omitted
Keywords: Iridium complex; Cyclometalated ligand; Phosphorescence; Near-infrared emission; Organic light-emitting diode;

Stabilization of G-quadruplex DNA and antitumor activity by different structures of nickel (II) complexes by Fangling Le; Dongdong Sun; Du Liu; Chuping Zheng; Ying Liu; Jie Liu (20-27).
In the present investigation, four nickel (II) complexes [Ni(bpy)3]2 + NB, [Ni(phen)3]2 + NP, [Ni(bpy)2(p-ipip)]2 + NBH and [Ni(phen)2(p-ipip)]2 + NPH were synthesized and characterized by electrospray ionization-mass spectrometry, where phen is 1,10-phenanthroline, bpy is 2,2′-bipyridine and p-ipip is 2-(4-indole)-imidazo[4,5f][1,10] phenanthroline. The interactions of human telomeric G-quadruplex DNA with these designed complexes were evaluated by CD spectroscopy, fluorescence resonance energy transfer (FRET) melting assay and FRET competitive binding experiment. The experimental evidence indicated that all complexes could strongly bind to and effectively stabilize the telomeric G-quadruplex DNA. Complex NPH was a better G-quadruplex binder than other complexes. Furthermore, polymerase chain reaction (PCR)-stop assay, gel mobility shift assay and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay demonstrated that complex NPH not only can stabilize dimers forms of the G-quadruplex at low concentrations but also high inhibitory selectivity against cancer cells. The results suggest that complex NPH may be a potential telomerase inhibitor for cancer chemotherapy.The scheme is the illustration of the Ni(II) complex NPH which is able to induce the HTG21 DNA into a mixed-type or hybrid G-quadruple and dependently stabilize the G-quadruplex.Display Omitted
Keywords: Ni (II) complex; DNA; Quadruplex structures; Anticancer activity;

The new ruthenium (II) phosphine complexes (η6-C6H6)RuCl2[μ- (PPh2CH2N)2CH2(C10H6)]RuCl26-C6H6) (1) and RuCl2(PPh3)[(PPh2CH2N)2CH2(C10H6)] (2) were synthesized and characterized by 1H NMR, 31P {1H} NMR and elemental analysis. Moreover, the structure of ruthenium (II) phosphine complex 1 was confirmed by X-ray crystallography. With complex 1 as the catalyst, the transfer hydrogenation of ketones reacted well, affording the corresponding alcohols in good yields under mild conditions.The new ruthenium (II) complexes based on a phosphine ligand 1,3-bis[(diphenylphosphanyl)methyl]-2,3-dihydro-1H-perimidine were synthesized and characterized. Both are valuable for the transfer hydrogenation of aromatic ketones.Display Omitted
Keywords: Ruthenium; Phosphine; Transfer hydrogenation; Ketone;

Hydrothermal reactions of N-(phosphonomethyl)proline (H3L) with nickel sulfate hexahydrate resulted in a novel nickel carboxylate–phosphonate: |H2O|[Ni3(O3PCH2–NC4H7–CO2)2(H2O)4] (complex 1). Single-crystal X-ray diffraction analysis revealed that complex 1 crystallizes in the triclinic space group P-1 (No. 2), with lattice parameters of a  = 10.0167(5) Å, b  = 10.3882(5) Å, c  = 11.9528(5) Å, α  = 90.132(3)°, β  = 107.246(3)°, γ  = 111.158(3)°, V  = 1099.39(9) Å3, and Z  = 2. Complex 1 features a 2D layered structure. The structure contains alternating Ni-centered octahedra (Ni(1)O6, Ni(2)O5N and Ni(3)O5N) and O3PC tetrahedra linked to construct a layer with rhombohedral 12-MRs holes. The cyclopentylamine moieties of H3L were grafted onto the layer through coordination of CPO3, CO2 and (CH2)2NCH2 with central nickel atoms. These layers are stacked in an AA sequence, which results in a one-dimensional channel in the [001] direction. Water molecules are located in these channels. Magnetic studies showed that complex 1 exhibits predominantly paramagnetic behavior.A novel nickel carboxylate–phosphonate with a layer structure: synthesis, crystal structures and magnetic properties.Display Omitted
Keywords: Hydrothermal synthesis; Structural characterization; Nickel carboxylate–phosphonate; Paramagnetic;

By employing 1,1′-biphenyl-3,3′-dicarboxylic acid (3,3′-H2BPDA) as a bridging ligand, a novel acentric heterometallic inorganic–organic hybrid framework [Cd3Na4(3,3′-BPDA)5(DME)7]·DME (1) has been synthesized. Single crystal X-ray diffraction study reveals that 1 contains an unusual 1D {Cd3Na4} n motif which is further extended into a 2-fold interpenetrating layer by trans-coordinated 3,3′-BPDA2 − ligands. Compound 1 is NLO active with a SHG effect being 0.5 times that of KDP. Besides, it also displays a potential ferroelectric property.A new acentric Cd(II)/Na(I) inorganic–organic hybrid framework, exhibiting both NLO and ferroelectric properties, was synthesized. This compound contains novel 1D {Cd3Na4} n arrays which are bridged by trans-3,3′-BPDA2 − ligands to form a 2-fold interpenetrating layer structure.Display Omitted
Keywords: Inorganic–organic hybrid material; Acentric framework; NLO; Ferroelectric property;

A new VHPO mimicking oxovanadium(IV) complex [VO(sal-l-val)(phen)] (sal-l-val = Schiff base derived from salicylaldehyde and l-valine; phen = 1,10-phenanthroline) has been synthesized and characterized by elemental analysis, UV–vis, IR spectroscopy, ESI-MS, EPR and single crystal XRD studies. The structural and spectral parameters were further supported using DFT calculations. The complex was found to exhibit vanadium dependent haloperoxidase (VPHO) activity.A new oxidovanadium complex [VIVO(sal-l-val)(phen)] has been designed and synthesized with the aim of developing active biocatalyst. The compound mimics the VHPO activity by effecting in vitro bromination of olefinic alcohols to the corresponding brominated products with good efficiency. The mechanism of catalytic activity has been established and confirmed by ESI-MS mass spectrometry.Display Omitted
Keywords: Oxovanadium(IV) complex; Single crystal XRD; DFT calculations; Haloperoxidase activity; Bromination of olefinic alcohols; Catalytic activity;

A new Cu(I) polymer, namely [Cu3(N3)3(MA)]n (1 MA = melamine) was prepared by the hydrothermal reactions of CuCl with NaN3 in the presence of melamine. Single-crystal X-ray diffraction analysis reveals that 1 features a three-dimensional (3D) pillar-layered framework, which can be simplified into a (3, 7)-connected topological network with the Schläfli symbol of {42.6}{46.615}. Interestingly, in this framework, three Cu(I) ions are connected together by three azide anions into an unusual [Cu3(N3)3] metallocycle building block. Under the direction of N―H…N hydrogen bonds, melamine ligand adopts a rare μ 3-bridging mode, and connects adjacent [Cu3(N3)3] metallocycles into a honeycomb two-dimensional (2D) layer. In addition, the catalytic performance of 1 for degradation of methyl orange in a Feton-like process has also been investigated.Presented here is a new Cu(I) coordination polymer constructed from mixed ligands of melamine and azide, which features a three-dimensional (3D) pillar-layered framework, and can be simplified into a (3, 7)-connected topological network with the Schläfli symbol of {42.6}{46.615}.Display Omitted
Keywords: Cu(I); Hydrothermal reaction; Pillar-layered framework; Catalytic performance;

Synthesis, structure and magnetic properties of a 3D anionic framework based on butterfly Ni4 clusters by Ying Zhao; Lu-Fang Ma; Zhen-Zhen Shi; Min-Le Han; Li-Ya Wang (50-53).
A 3D MOF {[Ni(H2O)6][Ni4L23-OH)2(H2O)2]}n (1) with a (4,8)-connected flu net is constructed by a butterfly-like tetranuclear [Ni43-OH)2(COO)8]2 − anionic cluster and organic linker 2,3′,5,5′-biphenyl tetracarboxylic acid (H4L). The disordered [Ni(H2O)6]2 + cations fill in the free voids of anionic framework in 1. Magnetic susceptibility measurements indicate that complex 1 shows weak antiferromagnetic interactions.Hydrothermal reactions of NiII salt with 2,3′,5,5′-biphenyl tetracarboxylic acid afford a (4,8)-connected 3D flu net, which contains butterfly-like tetranuclear [Ni43-OH)2(COO)8]2 − anionic clusters and disordered [Ni(H2O)6]2 + cations fill in the voids of anionic framework.Display Omitted
Keywords: NiII complex; 2,3′,5,5′-Biphenyl tetracarboxylic acid; Magnetic properties;

Syntheses, crystal structures and magnetic properties of two 2D copper–nitroxide coordination polymers bridged by flexible aliphatic dicarboxylate ligands by Dong-Zhao Gao; Hai-Xia Wei; Xiu-Guang Wang; Zhong-Yi Liu; Ya-Qiu Sun; Guo-Ying Zhang; Yan-Yan Xu (54-57).
Two novel two-dimensional copper–nitroxide coordination polymers of formula [Cu2(NIT3Py)2(glu)2]n (1) and {[Cu2(NIT3Py)2(adip)2] · CH3OH · 0.5H2O}n (2) (NIT3Py = 2-(3′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, H2glu = glutaric acid and H2adip = adipic acid), have been synthesized and characterized structurally as well as magnetically. The crystal structures of both polymers contain the paddle-wheel binuclear Cu(II) units axially coordinated by NIT3Py ligands which are bridged by the flexible glutarate or adipate anions into the corrugated 2D sheets. Interestingly, complex 1 displays a 2D helical layer structure rarely found in metal–nitroxide systems. The magnetic measurements show the strong antiferromagnetic interactions in the binuclear Cu(II) units and weak antiferromagnetic interactions between copper ions and nitroxides.Two novel copper–nitroxide coordination polymers have been synthesized. Two complexes contain the paddle-wheel binuclear Cu(II) units axially coordinated by NIT3Py ligands which are bridged by the flexible dicarboxylate anions into the corrugated 2D sheets. Complex 1 displays a 2D helical layer structure rarely found in metal–nitroxide systems. The magnetism is discussed.Display Omitted
Keywords: Copper complex; Nitronyl nitroxide radical; Flexible dicarboxylate ligand; Magnetic properties;

A series of metal complexes with 3,4-dimethyl-5-(2-pyridyl)-1,2,4-triazole (L), trans-[CoL2(MeOH)2](ClO4)2 (1), trans-[NiL2(MeOH)2](ClO4)2 (2), trans-[CuL2(ClO4)2] (3) and trans-[CoL2(NCS)2] (4) have been synthesized, and their molecular structures determined by X-ray crystallography, UV, IR, TGA/DSC, powder XRD and elemental analyses. Structural analyses indicate that both complexes 1 and 2 have a pseudo-octahedral [MN4O2] core with two ClO4 ions in the trans position. While complexes 3 and 4 show a distorted octahedron containing two trans-coordinated anions in 3 with ClO4 but in 4 with NCS.C–H · · · π and π · · · π stacking interactions in metal complexes.Display Omitted
Keywords: Syntheses; Triazole; Crystal structures; Metal complexes;

Compound [(EEIM)NaCu(phth)2]n (1) (EEIM = 1,3-diethylimidazolium and phth = terephthalate) was synthesized by using the mixed ionic liquids of 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM]-BF4 and chiral 1-ethyl-3-methylimidazolium l -lactate as solvent. The sodium(I) ion deriving from the [EMIM]-BF4 with a small amount of Na(I) impurity incorporated into the structure is unprecedented. Compound 1 is a 3D anionic framework based on a unique rod shaped heterometallic copper(II)–sodium(I)-carboxylate secondary building unit, exhibiting a distorted pcu-(412  · 63) topology. It is interesting that the organic template of [EEIM]+ cation formed from an in situ reaction acting as extraframework charge-balancing species occupies the 1D rhombic channels of the 3D anionic framework. The roles of the ionic liquid in ionothermal synthesis and crystallization of 1 are briefly discussed.Compound [(EEIM)NaCu(phth)2]n (1) (phth = terephthalate) was ionothermally synthesized by using the mixed ionic liquids of 1-ethyl-3-methylimidazolium tetrafluoroborate ((EMIM)BF4) and chiral 1-ethyl-3-methylimidazolium l -lactate ((EMIM)- l -lactate). Compound 1 has a 3D anionic framework with pcu-(412  · 63) topology based on the rod shaped heterometallic Cu(II)–Na(I)-carboxylate SBUs.Display Omitted
Keywords: Ionothermal synthesis; Topology; Heterometallic coordination polymer; Crystal structure;

Construction of two 2-D lanthanide(III)-frameworks with triple-stranded double-helical character based on ligand 4-(benzimidazol-1-ylmethyl)benzoate by Jian Yang; Ming-Fang Wang; Hong-Guang Jin; Xu-Jia Hong; Qing-Guang Zhan; Ling-Zhi Zhao; Yue-Peng Cai (65-69).
Two new complexes based on 4-(benzimidazol-1-ylmethyl)benzoic acid (HL), (Sm2L6·H2O)n (1) and (LuL3)n (2), have been synthesized under the solvothermal condition and characterized by single-crystal X-ray diffraction, X-ray powder diffraction (PXRD), thermogravimetric analysis (TGA) and elemental analysis (EA) and IR spectra. The results show that both complexes are isomorphous and possess 2-D pillar-chained frameworks, consisting of 1-D triple-stranded double-helical (PPM/MMP) [Ln(η 2-O)(μ 2-OCO)2]n (Ln = Sm(1), Lu(2)) motif as chain and μ 3-(η 1:η 1:η 1)-bridging ligand L as pillar, though they have different space groups of triclinic P-1 for 1 and monoclinic P21/c for 2. Two complexes represent the first example of 2-D lanthanide compound containing 4-(benzimidazol-1-ylmethyl)benzoic acid as the sole ligand. Additionally, the photoluminescent property of 1 is also discussed.Two new 2-D pillar-chained lanthanide-organic frameworks containing equal amounts of left–left–right (MMP)- and right–right–left (PPM)-handed triple strand double-helical chains were successfully constructed from reaction of 4-(benzimidazol-1-ylmethyl)benzoic acid with Ln(NO3)3 under hydrothermal conditions.Display Omitted
Keywords: 2-D LnIII pillar-chained MOFs; Triple-stranded double helicity; 4-(Benzimidazol-1-ylmethyl)benzoate; Fluorescence;

Two isostructural 3D coordination polymers (CPs) {[M(L242)2](ClO4)2} n (MII = CdII for 1 and ZnII for 2) have been constructed from metal perchlorates and a tripyridyltriazole ligand 4-(4-pyridyl)-3,5-bis(2-pyridyl)-1,2,4-triazole (L242). The host framework of each CP comprises two interpenetrating lvt topological networks. Three types of 1D channels with different chirality (achirality and left-handed or right-handed helicity) are observed to hold the perchlorate guest anions. Interestingly, both CPs materials have the exclusive and irreversible anion-exchange behaviors for acetate (OAc), which however, are unavailable to chloride (Cl), fluoroborate (BF4 ), or nitrate (NO3 ) anion. CPs 1 and 2 also show ligand-based solid-state fluorescent emissions at room temperature.This work presents two isostructural 3D CdII and ZnII coordination polymers consisting of open host coordination framework and perchlorate anionic guest, which show the selective anion-exchange behaviors toward acetate in an irreversible way.Display Omitted
Keywords: Coordination polymer; Tripyridyltriazole ligand; Open framework; Selective anion-exchange; Acetate;

A turn-on Schiff-base fluorescence sensor for Fe3 + ion by Chang-Hung Chen; Pei-Ju Hung; Chin-Feng Wan; An-Tai Wu (74-77).
We synthesized a novel Schiff-based fluorescent receptor 2, and investigated its binding properties toward various metal ions. The receptor 2 exhibited a blue shift in emission band upon binding with Fe3 +. The receptor 2 exhibited a high association constant with submicromolar detection for Fe3 + in MeOH solution.Receptor 2 exhibits an “off-on-type” mode with high sensitivity in the presence of Fe3 + and a high association constant with submicromolar detection for Fe3 + in MeOH solution.Display Omitted
Keywords: Chemosensor; Fluorescence; Turn-on; Schiff-base;

The research of a new polyoxometalates based photosensitizer on dye sensitized solar cell by Jian-Sheng Li; Xiao-Jing Sang; Wei-Lin Chen; Lan-Cui Zhang; Zhong-Min Su; Chao Qin; En-Bo Wang (78-82).
Keggin-type polyoxometalates (POMs) based photosensitizer [(CH3)4N]5[PW11O39RhCH2COOH]∙6H2O (PW11Rh-COOH) was firstly explored for assembling the POMs sensitized solar cells (PSSC). Electrochemical measurement, UV–vis diffuse reflectance spectrum, Surface photovoltage spectrum, and X-ray photoelectron spectroscopy demonstrated that PW11Rh-COOH displayed higher photovoltaic response than that of other POMs because of the better visible-light response, energy level matching and higher carrier separation efficiency.Keggin-type polyoxometalates (POMs) based photosensitizer [(CH3)4N]5[PW11O39RhCH2COOH]∙6H2O (PW11Rh-COOH) was firstly explored for assembling the POMs sensitized solar cells (PSSC), which displayed higher photovoltaic response than that of other POMs because of the better visible-light response, energy level matching and higher carrier separation efficiency.Display Omitted
Keywords: Polyoxometalate; Functionalization; Photosensitizer; Solar cell; Photoelectric conversion;

A novel inorganic–organic hybrid molecule, [Cu(4,4′bipyH)3(4,4bipy)][HPW12O40]2.12H2O (1), has been hydrothermally synthesized and characterized by IR spectra, TG and single crystal X-ray diffraction analyses. Structural analysis reveals that the novel compound 1 composed of two Kegging polyoxoanion connected with Cu complex fragment forming a big molecule that extends in 3D via hydrogen bonding.Structure of [Cu(4,4′bipyH)3(4,4bipy)][HPW12O40]2.12H2O consists of two Kegging polyoxoanion connected with Cu complex fragment forming a big molecule that extends in 3D via hydrogen bonding.Display Omitted
Keywords: Hydrothermal; Keggin; Polyoxoanion; Hybrid;

The oxidative electropolymerization of [Fe(L)2](PF6)2 {L  = 4′-{[p-(N-butyl-N-phenyl)amino]-phenyl}-2,2′:6′,2″-terpyridine} has been conducted by continuous cycling of the working electrode potential from 0 to 1.8 V in 0.1 mol·L− 1 Bu4NClO4/CH3CN solution containing 5.0 × 10− 4  mol·L− 1 monomer. The purple hybrid polymer film exhibits a non-diffusional charge transfer behavior of Fe(III)/Fe(II) couple and an irreversible redox process of phenylamine moiety on the Pt working electrode, as well as high stability in monomer-free electrolytic solution. The film thickness is easily tuned by controlling the number of potential sweeping cycle, and the AC impedance of as-formed film increases with cycling number. Morphological characterization of the film on indium tin oxide (ITO) has been provided by scan electron microscopy (SEM). The donor–acceptor (D–A) polymer film on ITO shows a broad and red-shifted 1MLCT wave in the UV–vis spectrum and a clearly electrochromic behavior from purple to pale yellow with the times of 1.1 s for the coloration step and 2.2 s for the bleaching step, the optical contrast of 20.3% and the coloration efficiency of 164 C− 1·cm2.D–A metallopolymer film: The arylamine functionalized Fe(II)–terpyridine complex has been electrochemically deposited on ITO electrode to form a polymer film containing in-chain metal centers, which shows a clearly electrochromic behavior from purple to pale yellow.Display Omitted
Keywords: Electropolymerization; Fe(II)–terpyridine complex; Phenylamine; Metallopolymer; Electrochromism;

A high-connected self-penetrating network supported by pentanuclear cobalt(II) secondary building units by Xu-Dong Zhang; Ya-Meng Li; Jian-Dong Pang; Zhan-Feng Ju (92-95).
A 3D ten-connected self-penetrating network based on the pentacobalt(II) clusters, [Co5(1,4-ndc)4(OH)2(1,3-bix)2]n (1) (1,4-H2ndc = 1,4-naphthalenedicarboxylic acid; 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene), is synthesized and characterized. Topological analysis indicates that it has ile-364345362 network. The magnetic data reveals the dominant antiferromagnetic interactions between the Co(II) cations.A 3D ten-connected self-penetrating network based on the pentacobalt(II) clusters is synthesized and characterized, Topological analysis indicates that it has ile-364345362 network. The magnetic data reveals the dominant antiferromagnetic interactions between the Co(II) cations.Display Omitted
Keywords: High-connected; Pentanuclear cobalt; Crystal structure; Magnetic property;

Synthesis and catalytic properties of novel POM@TiO2 composite materials by Jun Zhang; Wei-Lin Chen; En-Bo Wang (96-99).
Donor–π-bridge–acceptor (D–π–A) type polyoxometalates (POMs) were self-assembled for the first time on the surface of titanium dioxide (TiO2) nanoparticles through the layer-by-layer (LBL) method. The obtained composite materials POM@TiO2 were characterized by Transmission electron microscopy (TEM), Fourier transform IR spectroscopy (FTIR), Raman spectrum and energy dispersive X-ray (EDX) spectroscopy. Catalytic properties of POM@TiO2 were also investigated by treating organic pollutants (typically, removal of 40 mL 20 mg L− 1 methylene blue (MB) by 10 mg POM@TiO2 was up to 99.5% within 3 min under ambient conditions and the photodegradation efficiency was obviously higher than bare TiO2 nanoparticles under irradiation).Novel composite materials based on D–π–A type polyoxometalates and TiO2 with excellent catalytic ability in treating organic pollutantsDisplay Omitted
Keywords: Polyoxometalates; Titanium dioxide; Composite materials; Catalyst; Layer-by-layer;

An unusual polythreaded coordination network self-assembled from 2D motifs with two distinct lateral arms by Juan Yang; Shi-Wei Yan; Xin Wang; Dong-Rong Xiao; Hua-Yi Zhang; Xiao-Lin Chi; Jin-Ling Zhang; En-bo Wang (100-103).
Self-assembly of the trigonal 1,3,5-benzenetricarboxylate (H3btc) and copper salt in the presence of large trigonal N-containing ligand yields a fascinating entangled network, [Cu(Hbtc)(Htpba)]·1.5H2O (1) (Htpba = 4-([4,2′:6′,4″-terpyridin]-4′-yl) benzoic acid). Compound 1 exhibits a novel (2D → 3D) polythreaded network that is first assembled from 2D layers with two types of lateral arms. By inspection of the structure of 1, it is believed that the trigonal ligands with uncoordinated groups acting as dangling lateral arms play an important role in the formation of polythreaded network. The magnetic properties of compound 1 have been studied in the temperature range 2–300 K.The title compound exhibits an interesting (2D → 3D) polythreaded network that is first assembled from 2D layers with two distinct lateral arms.Display Omitted
Keywords: Entangled network; Polythreading; Self-assembly;

A new porous 2D copper(II) metal–organic framework for selective adsorption of CO2 over N2 by Da-Shu Chen; Jia-Ming Cheng; Li-Bo Sun; Zhi-Qiang Liang; Kui-Zhan Shao; Chun-Gang Wang; Hong-Zhu Xing; Zhong-Min Su (104-107).
A new porous 2D metal–organic framework [Cu(L)DMF]·2H2O (1) has been synthesized by self-assembling copper paddle-wheel units with an asymmetrical dicarboxylate ligand prolonged by alkyne groups, 3,3′-(ethyne-1,2-diyl)dibenzoic acid (H2L) under solvothermal condition. The activated sample 1a displays selective adsorption of CO2 over N2 and shows low isosteric heat (Q st) of CO2 adsorption.A new porous 2D metal–organic framework has been synthesized by self-assembling copper paddle-wheel units with an asymmetrical dicarboxylate ligand prolonged by alkyne groups under solvothermal condition. The activated compound exhibits selective adsorption of CO2 over N2.Display Omitted
Keywords: Metal–organic frameworks; Asymmetrical ligand; CO2; Adsorption; Microporous;

A zinc(II) porphyrin complex bearing a bipyridine moiety at the periphery was synthesized. The singlet excited state of the complex was found to be quenched by Cu2 + in methanol, and the photoinduced electron transfer from the excited state of the porphyrin to the bipyridine moiety in the presence of excess Cu2 + ion was observed using a transient absorption technique. The relatively long lifetime of the charge-separated state was ascribed to the slow electron exchange reaction of Cu(II)/Cu(I) couple bound to the bipyridine unit.A zinc(II) porphyrin dyad bearing a bipyridine moiety was synthesized. A photoinduced electron transfer from the excited state of the porphyrin complex to the bipyridine unit was observed in the presence of Cu2 + in methanol.Display Omitted
Keywords: Zn(II) porphyrin dyad; Quenching; Charge-separated state;

Two fluorescence turn-on chemosensors for cyanide anions based on pyridine cation and the boronic acid moiety by Ruifang Guan; Huihui Chen; Fengxia Cao; Duxia Cao; Yunlong Deng (112-114).
Two chemosensors for cyanide anions based on N-methylpyridinium cation and the boronic acid moiety structures have been synthesized. Spectral shifts and intensity changes in acetonitrile allow for both absorption and fluorescence emission wavelength ratiometric and colorimetric sensing. The compounds are found to be able to recognize cyanide anion with obvious color change and fluorescence turn-on response due to the sensors' ability to bind the cyanide anion through boronic acid functional group.Two fluorescence turn-on chemosensors for cyanide anions based on pyridine cation and the boronic acid moiety were prepared and can recognize cyanide anion with obvious color change and fluorescence turn-on response.Display Omitted
Keywords: Boronic acid; Cyanide; Chemosensor; Pyridinium cation; Fluorescence change;

Three new metal–organic frameworks Mn(3,5-PDC)(H2O)•(glycol) (JUC-58), M(3,5-PDC)(H2O)(glycol)•(H2O) (JUC-59-M, M = Co, Ni), have been synthesized by the assembly of tri-connected ligand pyridine-3,5-dicarboxylic acid (3,5-PDC) and different metals under the solvothermal condition in DMF and glycol. JUC-58 is an unusual example of 3-D chiral MOF with helical channels, while JUC-59-Co and JUC-59-Ni are isostructural and have non-centrosymmetric structures with a very rare 3-connected non-interpenetrated lig-b net. It is worth noting that glycol could play an important role in the formation and stabilization of these networks.JUC-58 and JUC-59-Co, Ni were synthesized by pyridine-3,5-dicarboxylic acid and different metals under solvothermal condition in DMF and glycol. JUC-58 is homochiral, while JUC-59-Co, Ni have a lig-b net. It is worth noting that glycol could play an important role in the formation and stabilization of the MOFs.Display Omitted
Keywords: Metal–organic frameworks; Chiral; Non-centrosymmetric; Pyridine-3,5-dicarboxylate;

Synthesis, morphology, and upconversion luminescence of Tm3 +/Yb3 + codoped bulk and submicro-rod CaSc2O4 phosphors by Jing Li; Jiahua Zhang; Zhendong Hao; Xia Zhang; Jihong Zhao; Shaozhe Lü; Yongshi Luo (119-122).
CaSc2O4: Tm3 +/Yb3 + submicro-rods were synthesized using the mild solvothermal and annealing technique. The temperature of formed pure phase is as low as 600 °C. The synthesized submicro-rods are uniform in size and shape. The size of rod is only small with 35 nm in width and 200 nm in length, which favors the application in biological assays and medical image. Furthermore, samples prepared exhibit the stronger upconversion luminescence than that of obtained by conventional solid state reaction method under 980 nm excitation. The near infrared emission around 800 nm is enhanced twofold closely. CaSc2O4 phosphor synthesized through the solvothermal and annealing method is a promising submicron upconversion material. The solvothermal and annealing technique is a suitable method for preparing CaSc2O4 sample with rod-like morphology.The rod-like CaSc2O4: Tm3 +/Yb3 + phosphors were firstly synthesized using the mild solvothermal and annealing technique. The synthesized submicro-rods are uniform in size and shape of which the size is only small with 35 nm in width and 200 nm in length.Display Omitted
Keywords: Microstructure; Solvothermal; Upconversion luminescence; Oxides;

Novel polyoxometalates with an inverted-Keggin structure were prepared and isolated as the tetra-alkylammonium salts from an aqueous organic solution. They were characterized using elemental analysis, X-ray analysis, UV–vis, IR and Raman spectroscopy. This study demonstrates that these novel polyoxometalates with an inverted-Keggin structure could be used as a new building block material because they have both a carboxy group and an alkene part, which could react with other organic substrates.Novel polyoxometalates with inverted-Keggin structure were synthesized using a few types of organophosphates.Display Omitted
Keywords: Polyoxometalate; Inverted-Keggin; Organophosphate; Building block;

Addition of allyl halides to the new bis-o-amidophenolate gallium(III) complex by Alexandr V. Piskunov; Irina V. Ershova; Georgii K. Fukin; Andrei S. Shavyrin (127-130).
The synthesis and characterization of the new bis-o-amidophenolate gallium(III) complex are reported. This compound was found to be reactive towards allyl halides at room temperature. The addition of two allyl halide molecules to the original complex accompanied with two new C–C bonds formation has been observed. The structures of the products obtained were confirmed by 1H NMR and X-ray diffraction analysis.The synthesis and characterization of the new bis-o-amidophenolate gallium(III) complex is reported. This compound was found to be reactive towards allyl halides at room temperature. The addition of two allyl halide molecules to the original complex accompanied with two new C–C bonds formation has been observed. The structures of the products obtained were confirmed by 1H NMR and X-ray diffraction analysis.Display Omitted
Keywords: o-Amidophenolate; Gallium; Allyl halide; NMR spectroscopy; X-ray diffraction;

The coordination chemistry of the ligand 1-benzoyl-4,5-dihydro-3,5-bis(trifluoromethyl)-1H-pyrazol-5-ol (1a) has been recently investigated. In dependency of the metal (e.g., nickel, zinc, molybdenum) and the added co-ligand (phosphanes, pyridines, amines) different coordination modes were feasible (e.g., O,N,O′, O,N, O,O′). Herein we present the reaction of 1a with Cu(OAc)2 and triphenylphosphane as co-ligand to form the copper complex 2 [Cu(1a-H)(PPh3)2]. The complex was characterized and investigated by various techniques, pointing out a new bidentate coordination mode of the ligand. In more detail, X-ray crystallography determined a N,O-coordination in which the ligand is planar and the other coordination sites on the copper centre are occupied by two PPh3 creating a tetrahedral coordination geometry. Moreover, the complex has been applied as precatalyst in the copper-catalyzed amination of aliphatic C–H bonds.The coordination chemistry of the ligand 1-benzoyl-4,5-dihydro-3,5-bis(trifluoromethyl)-1H-pyrazol-5-ol (1a) has been recently investigated. In dependency of the metal (e.g., nickel, zinc, molybdenum) and the added co-ligand (phosphanes, pyridines, amines) different coordination modes were feasible (e.g., O,N,O′, O,N, O,O′). Herein we present the reaction of 1a with Cu(OAc)2 and triphenylphosphane as co-ligand to form the copper complex 2 [Cu(1a-H)(PPh3)2]. The complex was characterized and investigated by various techniques, pointing out a new bidentate coordination mode of the ligand. In more detail, X-ray crystallography determined a N,O′-coordination in which the ligand is planar and the other coordination sites on the copper centre are occupied by two PPh3 creating a tetrahedral coordination geometry. Moreover, the complex has been applied as precatalyst in the copper-catalyzed amination of aliphatic C-H bonds.Display Omitted
Keywords: Copper; N,O-ligand; Phosphane ligands; DFT calculations; Catalysis;

Synthesis and thermotropic behavior of cholesteric mixtures containing metallomesogen Cu(II), Ni(II), Pd(II) and vanadyl complexes by Fabio Borbone; Antonio Carella; Giuseppina Roviello; Laura Ricciotti; Barbara Panunzi; Michelina Catauro; Antonio Roviello (135-138).
In this work the synthesis of a series of Ni(II), vanadyl and Pd(II) metallomesogen complexes with a chiral ligand is reported. Cholesteric mixtures were obtained by mixing such complexes with analogous achiral complexes and their thermotropic behavior was studied by means of differential scanning calorimetry, temperature dependent UV–Visible spectroscopy and optical observation. The results show a strong dependence of the cholesteric pitch on the temperature for Ni/Ni mixtures, minor and no dependence respectively for VO/VO and Pd/Pd mixtures, this last in accordance with the known behavior of Cu/Cu mixtures. The study reveals an influence of the metal and its coordination geometry on the temperature dependence of the cholesteric pitch.The LC behavior of cholesteric mixtures of Cu(II), Ni(II), VO(II), Pd(II) chiral and achiral complexes was studied. A strong dependence of the cholesteric pitch on the temperature for Ni based mixtures was revealed.Display Omitted
Keywords: Cholesteric LC; Variable pitch; Reflective film; Nickel; Vanadyl;

Structure regulation of Nickel (II) complexes with imidazole–tripodal ligand by altering the counter anions and the reaction conditions by Yan An; Xiao-Feng Li; Yu-Liang Zhang; Yan-Sheng Yin; Jing-Jia Sun; Shi-Fang Tong; Hong Yang; Shi-Ping Yang (139-142).
For the reaction products of N,N-bis(2-(1-methylimidazolyl)methyl)glycine (HL) with nickel (II), the conversion from a mononuclear complex of [NiL(H2O)2]NO3  · CH3OH (1) to a trinuclear complex of [NiL(H2O)2][Ni(H2O)4(CH3O)2]2(SO4)2  · (H2O)2 (2) was achieved by altering the types of the counter anions and the pH value of the reaction system. The coordination structures were studied by single-crystal X-ray analysis. The electrochemical and magnetic properties were measured to reveal the structure–property relationship.Mononuclear and trinuclear complexes of Ni(II) with an unsymmetry tripodal ligand derived from imidazole could be achieved by altering the counter anions and the pH value of the reaction system. The electrochemical and magnetic properties were measured to reveal the structure–property relationship.Display Omitted
Keywords: Imidazole–tripodal ligand; Crystal structure; Electrochemical property; Magnetic property;

The iron carbonyl thionyl Fe2(SO)(CO)8 is predicted by density functional theory to have a triply bridged structure analogous to Fe2(CO)9. However, it is disfavored by more than 30 kcal/mol with respect to CO2 elimination to give Fe2(S)(CO)7, predicted to have a very unsymmetrical bridging sulfur atom forming an FeS triple bond with one iron atom and a Fe―S single bond with the other iron atom.The iron carbonyl thionyl Fe2(SO)(CO)8 is predicted by density functional theory to have a triply bridged structure analogous to Fe2(CO)9. However, it is disfavored by more than 30 kcal/mol with respect to CO2 elimination to give Fe2(S)(CO)7, predicted to have a very unsymmetrical bridging sulfur atom.Display Omitted
Keywords: Iron; Metal thionyls; Carbon dioxide elimination; Iron carbonyl sulfides; Density functional theory;

Solvothermal reactions of the less-noble metals Mn, Fe, and Zn with elemental sulfur or/and selenium in liquid ammonia or methylamine give a series of polyselenides and polysulfides, namely [Mn(NH3)6]Se3 (1), [Mn(MeNH2)6]Se4 (2), [Mn(NH3)6]S6 (3), [Fe(NH3)6]S6 (4), [Zn(NH3)6]S6 (5), [Mn(NH3)6]Se6 (6), [Fe(NH3)6]Se6 (7) and two mixed sulfideselenides [Mn(MeNH2)6](S5)0.15(S1.57Se2.43)0.85 (8) and [Mn(NH3)6](S2.71Se2.29) (9). All compounds represent ionic structures with octahedral [M(NH2R)6]2 + (M = Mn, Fe, Zn; R = H, CH3) complex cations and various polychalcogenide anions in the form of chains consisting of three to six sulfur and/or selenium atoms. The hexachalcogenides 47 are isostructural. In the structure of 8  S5 2 − and (S/Se)4 2 − anions are present in 15%: 85% ratio on one crystallographic site. 9 contains a (S/Se)5 2 − mixed chalcogenide anion. Generally, N–H∙∙∙S/Se bonding is weak, which facilitates the observed disorder of the polychalcogenide chains in the hexachalcogenides 47. The structures of 18 show a packing of cations and anions of the simple rock-salt structure type while 9 adopts the PtS structure type.Solvothermal reactions of the less-noble metals Mn, Fe, and Zn with elemental sulfur or/and selenium in liquid ammonia or methylamine give a series of polyselenides and polysulfides. All compounds represent ionic structures with octahedral [M(NH3)6]2 + and [M(NH2CH3)6]2 +complex cations (M = Mn, Fe, Zn) and various polychalcogenide anions in the form of chains consisting of three to six sulfur and/or selenium atoms.Display Omitted
Keywords: Polysulfides; Polyselenides; Ammine complexes; Methylamine complexes; Solvothermal synthesis;

A novel triruthenium metal string complex with naphthylridylamide ligand: Synthesis, structure, magnetism, and molecular conductance by Cherng-Shiaw Tsai; Isiah Po-Chun Liu; Fang-Wei Tien; Gene-Hsiang Lee; Chen-Yu Yeh; Chun-hsien Chen; Shie-Ming Peng (152-155).
A triruthenium metal string, [Ru3(npa)4(NCS)2][PF6] (1), supported by naphthylridylamide (npa) ligands was successfully synthesized and is reported in this work. X-ray single crystal analysis shows that compound 1 exhibits a nonlinear [Ru3]7 + backbone (∠ = 170.26(3)°) with long Ru–Ru bond lengths (2.3554(8) Å). The long Ru–Ru distances observed for 1 decrease the Ru–Ru interactions and electric conductance. Magnetic measurements indicate that compound 1 is in a S = 1/2 state. DFT calculations suggest that this unpaired electron occupies the π orbital which is stabilized by π-acid NCS ligands and thus weakening the Ru–Ru π interaction.A novel triruthenium metal string complex supported by naphthylridylamide ligands was synthesized and structurally characterized by X-ray single crystal diffraction.Display Omitted
Keywords: Ruthenium; Molecular wire; Metal–metal interaction; Molecular conductance;

Aldehyde coordination in template reactions: Crystal structure of a possible reaction intermediate by Mi Seon Won; Young Hoon Lee; Elisabeth Rukmini; Jack M. Harrowfield; Yang Kim (156-159).
The aldehyde complex [Zn(Im4al)2(NO3)2], where Im4al = imidazole-4-aldehyde (N(1)H tautomer), crystallises from methanol as a monoclinic species, space group C2/c, a 15.890(3), b 6.8920(14), c 14.077(3) Å, β 119.67(3) °. Its structure solution shows that the aldehyde–O donors are situated relatively distant (2.57(2) Å) from the metal ion centre, creating uncertainty as to whether the metal should be described as 4- or 6-coordinate. The seemingly very weak interaction of the aldehyde–O atoms with the Zn(II) indicated by the calculation of the Hirshfeld surface for the molecule in its lattice is consistent with the fact that this metal ion does not favour hydration of the aldehyde in aqueous solution. It may indicate that the role of the metal ion in template reactions involving the aldehyde and amines is to poise the aldehyde–C between its “unactivated”, and probably quite differently solvated, free state and a second state which is not sufficiently activated to favour addition of solvent water (or methanol) but which is activated sufficiently to undergo rapid addition of an amine nucleophile.The crystal structure of potentially chelating imidazole-4-aldehyde when bound to zinc(II) shows that the aldehyde is bound through imidazole-N only, indicating that activation of the aldehyde in template reactions may not be due to direct polarisation of the carbonyl group.Display Omitted
Keywords: Aldehyde coordination; Crystal structure; Template effect;