Inorganic Chemistry Communications (v.14, #1)

Contents List (iii-xxv).

A new anionic species [HgBr4Cl]3− has been isolated in the form of complex salt, [Co(NH3)6][HgBr4Cl] (1). The complex salt was crystallized from a solution of hexamminecobalt(III) chloride and potassium tetrabromidomercurate(II) in aqueous medium in 1:1 molar ratio. This complex salt has been characterized by elemental analyses, spectroscopic techniques (e.g. UV/Visible, IR), solubility product and conductance measurements. The complex salt crystallizes in monoclinic crystal system with space group P21/c. Single crystal X-ray structure determination revealed the presence of discrete ions: [Co(NH3)6]3+ cation and a new anion [HgBr4Cl]3−. This is the first structural report of any complex salt containing mixed halogenidomercurate(II) ion, [HgBr4Cl]3−. The crystal lattice is stabilized by the extensive hydrogen bonding (N―HBr/Cl) between the cationic and anionic moieties resulting in a bi-layered structure.A new mixed halogenidomercurate(II) ion, [HgBr4Cl]3− has been isolated in the form of complex salt, [Co(NH3)6][HgBr4Cl], characterized by spectroscopic techniques and single crystal X-ray structure determination. This is a first structural report of the anion [HgBr4Cl]3−. The crystal lattice is stabilized by the extensive hydrogen bonding (N―H Br/Cl) resulting in a bi-layered structure.Display Omitted
Keywords: Cobalt(III); Coordination chemistry; Tetrabromidochloridomercurate(II); X-ray crystallography;

Synthesis and structure elucidation of new series of organotin(IV) esters with bio-screening activity and catalytic study by Muhammad Ashfaq; M. Mahboob Ahmed; Salma Shaheen; Hiroyuki Oku; Karamat Mehmood; Abdullah Khan; Shahida Begum Niazi; Tariq Mahmood Ansari; Abdul Jabbar; M.I. Khan (5-12).
A new series of fourteen numbers of organotin(IV) esters with NNDEG and NNDBG is being described. On the basis of IR, 1H-, 13C-NMR, Mass and Mössbauer spectroscopic studies and elemental analysis data, an interesting sinusoidal view of dimeric organotin(IV) is proposed and octahedral geometry is suggested for monomeric organotin(IV) esters while triorganotin(IV) complexes are assigned trigonal bipyramidal and tetrahedral geometry which is confirmed by 1H NMR. All the OTCs except 1, 4, 8 and 10 exhibited excellent rate of mortality against selected insects. OTCs (2, 6, 9, and 11) at 500 ppm showed a two-fold positive role than standard drug Enoxacin as an antibiotic against the selected bacterial strains. ED50 of all OTCs is also reported here. The catalysis study of monomeric OTCs give 80% yield while dimeric OTCs give 100% yield of benzylacetate in six hours of reaction time.The new series of monomer, dimer and triorganotin(IV) esters have been synthesized. An interesting sinusoidal view of dimeric organotin(IV) is proposed and octahedral geometry is suggested for monomeric organotin(IV) while triorganotin(IV) esters are assigned trigonal bipyramidal and tetrahedral geometry. Mostly OTCs exhibited excellent insecticidal activity and two-fold positive role than standard drug Enoxacin. The catalysis study of mono and dimeric OTCs give 80–100% yield of benzylacetate.Display Omitted
Keywords: NN-diethylglycine (NNDEG); NN-dibutylglycine (NNDBG); Organotin compounds (OTCs); Tri Organotin compounds (TOTCs);

Color difference caused by chirality by Zhaoqiong Jiang; Hua Lu; Di Wu; Xiangge Zhou; Zhen Shen; Nagao Kobayashi (13-16).
Synthesis, crystal structure and spectra properties of enantiopure and corresponding racemic Cu(II)-dipyridine amido complexes are reported. The different coordination styles result in the unexpected chiral-unrelated color changes between chiral and racemic complexes.Molecular packing in the crystal of the racemic-1. (R,R) and (S,S) molecules pack alternately with intermolecular Cu–O bond length of 2.451 Å.Display Omitted► Chiral-unrelated optical properties could be affected by molecular chirality. ► A racemic and corresponding Enantiopure complex showed different color in crystal. ► The color difference came from the different coordination style of Cu.
Keywords: Chiral coordination complex; Color; Crystal structure; Copper;

The paper presents a combined experimental and computational study of the dinuclear oxorhenium(V) complex incorporating 4,5-diaza-fluoren-9-one (dafone). The complex has been studied by IR, UV–vis spectroscopy and X-ray crystallography. The electronic structure of [Re2O3Br4(dafone)2] has been calculated with the density functional theory (DFT) method, and the electronic spectrum of the complex was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ.A dinuclear oxorhenium(V) complex incorporating 4,5-diazafluoren-9-one was synthesized and studied by IR, UV–vis and X-ray. The electronic structure of [Re2O3Br4(dafone)2]·2THF was calculated with the density functional theory method, and the electronic spectrum of the complex was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ.Display Omitted► A dinuclear oxorhenium(V) complex. ► A prefect linear Re2O3 4+ core. ► Triple bond between the Re and Ot ligand.
Keywords: Oxorhenium(V) complexes; 4,5-Diazafluoren-9-one; X-ray structure; UV–vis spectrum; DFT and TDDFT calculations;

Construction of a cadmium supermolecular compound from 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid by Xuemin Jing; Tingting Zhao; Bing Zheng; Yu Peng; Yan Yan; Qisheng Huo; Yunling Liu (22-25).
A cadmium compound [Cd(C10H5N3O4)(H2O)2] 1, based on 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H3PyImDC) has been solvothermally synthesized and characterized. Single-crystal structural analysis reveals that the compound crystallizes in the orthorhombic system, Pna21 space group with a  = 6.8293(14) Å, b  = 12.331(3) Å, c  = 13.732(3) Å, V  = 1156.3(4) Å3 and R 1  = 0.0257. In compound 1, two nitrogen and two oxygen atoms of the H3PyImDC ligand coordinate to two Cd2+ ions to form a straight chain which then pack with each other via strong π–π and hydrogen-bondings interactions to construct a three-dimensional (3D) supermolecular structure. Further characterization of compound 1 was performed by X-ray powder diffraction (XRD), thermal gravimetric analyses (TG), infrared (IR) spectra, inductively coupled plasma (ICP) and elemental analyses. The fluorescent property was also evaluated.A supermolecular structure based on 2-(pyridine-3-yl)-4,5-imidazoledicarboxylic acid, with high hydrothermal stability and strong florescent emissions for its strong π–π and hydrogen-bondings interactions, has been synthesized and characterized.Display Omitted
Keywords: Solvothermally synthesized; Hydrogen-bondings; Supermolecular; Metal-organic frameworks;

Synthesis, characterization of sodium and potassium complexes and the application in ring-opening polymerization of L-lactide by Longhai Chen; Lei Jia; Feixiang Cheng; Lei Wang; Chu-chieh Lin; Jincai Wu; Ning Tang (26-30).
A novel sterically bulky phenol (2,4-di-tert-butyl-6-(1-(3,5-di-tert-butyl-2-(2-(2-methoxyethoxy)ethoxy)phenyl)ethyl)phenol)(HL) and corresponding dimeric sodium and potassium complexes [ML]2 (1: M  = Na, 2: M  = K) have been prepared and structurally characterized. Experimental results showed that complexes 1 and 2 can efficiently initiate the ring-opening polymerization of lactide in a controlled fashion, yielding polymers with expected molecular weight and low polydispersity indexes.Two new dimeric sodium and potassium complexes [ML]2 (1: M  = Na, 2: M  = K) have been synthesized and structurally characterized, which serve as catalysts in the ring-opening polymerization of lactide. Experimental results showed that two complexes are effective catalysts for the ROP of lactide in a controlled fashion, yielding polymers with expected molecular weight and low polydispersity indexes.Display Omitted► Two new nontoxic sodium and potassium complexes have been designed and synthesized. ► The catalytic activities of catalysts for ROP of lactides have been investigated. ► The positive experimental results showed that two complexes are excellent catalysts. ► Good controlled manner with slight isotactic selectivity has been gotten by catalysts.
Keywords: Sodium; Potassium; Catalyst; Lactide; Ring-opening polymerization;

Using dissymmetrical copper(II) precursor, [Cu(oxbe)]2−, a novel coordination polymer, namely {[Cu(cis-oxbe)]2[Cu(trans-oxbe)]2CuNa2(DMF)2}n (1) (oxbe =  N-benzoate-N′-(2-aminoethyl)oxamido) has been synthesized and characterized by IR, elemental analysis, X-ray crystal diffraction and magnetic properties. Single-crystal structural analysis shows that complex 1 consists of 3D framework containing both cis-oxamidato bridges and trans-oxamidato bridges, which is the first example that cis- and trans-oxamidato occur in the same structure. Its magnetic properties have also been investigated.Display Omitted
Keywords: Oxamidate ligands; Crystal structure; Magnetic properties;

A new coordination polymer, H[{Ce(H2O)5}2{Ce(pdc)2(H2O)4}{Ce(pdc)3}(PW12O40)]•2H2O 1 (pdc = pyridine-2,6 -dicarboxylate), has been obtained by the hydrothermal reaction. It exhibits a 3D hydrotalcitelike structure constructed from 2D cationic [{Ce(H2O)5}2{Ce(pdc)2(H2O)4}{Ce(pdc)3}]2+ layers pillared by α-Keggin [PW12O40]3− anions. Polymer 1 is active for photocatalytic H2 evolution under UV irradiation.Polymer 1 exhibits a POM-pillared hydrotalcitelike structure and it is active for photocatalytic H2 evolution.Display Omitted
Keywords: Polyoxometalate; Hydrothermal synthesis; Ce(III) polymer; Crystal structure; Photocatalysis;

Pillow-shaped porous CuO as anode material for lithium-ion batteries by Mei Wan; Dalai Jin; Ran Feng; Limin Si; Mingxia Gao; Linhai Yue (38-41).
Pillow-shaped porous cupric oxide (CuO) was prepared by a template-free method. Highly crystallized CuC2O4 precursor with micron-size in high dispersivity was prepared through a hydrothermal method first. Thermal treatment was carried out with the obtained precursor to produce porous cupric oxide. Thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and galvanostatic cell cycling were employed to characterize the structure and electrochemical performance of the porous cupric oxide. The porous CuO powder exhibited high average coulombic efficiency (98.3%) and capacity retention (83.3% of the discharge capacity of the second cycle after 50 cycles) at a current rate of 0.1 C.Pillow-shaped porous cupric oxide was obtained by the controlled thermal decomposition of the precursor CuC2O4. The as-prepared CuO electrode exhibits an initial discharge capacity of 770.3 mAh.g–1 with the average coulombic efficiency of 98.3% and 83.3% retention of the discharge capacity of the second cycle after 50 cycles.Display Omitted►Pillow-shaped porous cupric oxide (CuO) was prepared by a template-free method. Micron-size CuC2O4 crystal was first prepared by a simple hydrothermal chemical route. Porous cupric oxide was then obtained by the controlled thermal decomposition of the precursor CuC2O4. ►The porous CuO was assembled by nanocrystallines with size of about 30 nm. ►The as-prepared CuO electrode exhibits an initial discharge capacity of 770.3 mAh g− 1 with the average coulombic efficiency of 98.3% and 83.3% retention of the discharge capacity of the second cycle after 50 cycles.
Keywords: Porous cupric oxide; Thermal decomposition; CuC2O4 precursor; Electrochemical performance;

From molecular wires to potential molecular cables by Alexandrina Stuparu; Matthias Fischer; Olaf Fuhr; Oliver Hampe; Christophe Stroh (42-45).
Triple-helices with additional functional groups for anchoring on metal electrodes are accessible via metal-coordination assisted self-assembling.Triple-helices with additional functional groups for anchoring on metal electrodes are accessible via metal-coordination assisted self-assembling.Display Omitted
Keywords: Helicate; Heterocycle; Coordination compound; Crystal structure;

Two aminobenzothiazole derivatives for Pd(II) and Zn(II) coordination by Ugo Caruso; Barbara Panunzi; Antonio Roviello; Marco Tingoli; Angela Tuzi (46-48).
Two derivatives of 2-aminobenzothiazole are reported: an imine potentially able to generate on deprotonation a mononegative ligand moiety and an amide suited to metal coordination. Both have been used for producing tetracoordinated complexes of zinc (II) and palladium (II). The thermodynamic and optical properties of ligands and complexes were analysed by calorimetry, polarizing microscopy and an X-ray technique. In particular, the fluorescence properties of ligands and complexes were explored.Preparation and properties of two 2–aminobenzothiazole derivatives are reported: one imine potentially able to generate a mononegative ligand moiety and one amide suited to metal coordination. Both have been used for producing tetracoordinated complexes of zinc (II) and palladium (II). Fluorescence properties of ligands and complexes were analysed.Display Omitted
Keywords: Benzothiazole; Zn(II) complex; Pd(II) complex; Crystal structure; Fluorescence;

The self-assembly reaction of the flexible ligand 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (ttmb), Cd(II) and dca (dicyanamide) gives a novel coordination polymer {[Cd(ttmb)(dca)2]•H2O}n (1). There are two kinds of dca ligands (the bis-monodentate bridging dca and the monodentate dca). Each bridge ligand ttmb links three Cd(II) atoms to form a two-dimensional (6, 3) network [Cd(ttmb)]n. The bridge dca ligands further connect the two-dimensional networks to construct a novel (2,3,5)-connected three-dimensional network. Two identical three-dimensional networks interpenetrate each other giving rise to a double interpenetrating network. 1 exhibits blue luminescent emission maxima at 383 nm in the solid state at room temperature.Each ttmb links three Cd(II) atoms to form a two-dimensional (6, 3) network [Cd(ttmb)]n. The bridge dca ligands further connect the two-dimensional networks to construct a novel (2,3,5)-connected three-dimensional network. Two identical three-dimensional networks interpenetrate each other giving rise to a double interpenetrating network.Display Omitted►Slow diffusion reaction gives a novel coordination polymer. ►Each ligand ttmb links three Cd(II) atoms to form a 2D (6, 3) network. ►The bridge dca ligands connect the 2D networks to construct a novel 3D network. ►Two identical 3D networks interpenetrate each other. ►Complex 1 exhibits blue luminescent emission maxima at 383 nm.
Keywords: Interpenetrating network; (2,3,5)-Connected; Three-dimensional network; Two dimensional (6, 3) network; Cadmium complex; 1,3,5-Tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene;

Reaction of Cd(SO4)2 •6H2O with 1,4-bis(1,2,4-triazol-1-yl)butane (btb) gave a novel addition complex {[Cd2(btb)2(H2O)6(SO4)][Cd(btb)(H2O)2(SO4)2]2H2O}, which was characterized by single crystal X-ray diffraction. The complex composes of 1D cationic double chain and 1D anionic single chain constructed from btb–Cd–SO4 building blocks. The single and double chains are mutually interpenetrating to construct a 3D supramolecular network by inter-chain hydrogen bonds. The fluorescence of the complex is assigned to the intraligand π–π transition of the ligand.A novel addition complex {[Cd2(btb)2(H2O)6(SO4)][Cd(btb)(H2O)2(SO4)2]2H2O} composes of 1D cationic double chain and 1D anionic single chain based on btb–Cd–SO4 building blocks. The single and double chains are mutually interpenetrating to construct a 3D supramolecular network by inter-chain hydrogen bonds.Display Omitted► A novel addition complex compose of 1D cationic double chain and 1D anionic single chain constructed from btb-Cd-SO4 building blocks. ► The single and double chain with the different chemical compositions. ► Single and double chains are interpenetrating to construct a 3D supramolecular network via inter-chain hydrogen bonds. ► A new interpenetration motif was presented.
Keywords: Cadmium; 1,4-Bis(1,2,4-triazol-1-yl)butane; Addition complex; Crystal structure; Luminescence;

In this research, the synthesis, structure and magnetic properties of an ion-pair complex {[MnII(hmp)2]2(Cl)2}{[MnII(hmp)2WV(CN)8]2} (1) (hmpH = 2-hydroxymethylpyridine) are reported. Complex 1 was prepared by [W (CN)8]3− reacting with Mn(II) salt and hmpH in MeCN solution. Single-crystal X-ray diffraction shows that 1 is crystallized in triclinic system with a space group of P-1 and its structure consists of four parts of two chlorine-bridged [Mn2] cations and two tetrameric [Mn2W2] anionic clusters. The cationic [Mn2] and anionic [Mn2W2] moieties each are connected by π–π stacking to form their own layer. The packing of cations and anions layer by layer via molecular electrostatic potential, Van der Waals force and hydrogen bonding constructs a three-dimensional supramolecular framework. The magnetic analyses show the antiferromagnetic coupling interaction between MnII and WV or MnII and MnII in both parts. No evidence of single-molecule magnet or long-range ordering is observed in the data. By comparing to an analog with spin glass properties, we draw a conclusion that the differences of crystal packing mode, especially the π–π stacking within each layer, could be a key factor for the distinct magnetic properties.Ion-pair complex of {[MnII(hmp)2]2(Cl)2}{[MnII(hmp)2WV(CN)8]2} (hmpH = 2-hydroxymethylpyridine) with square construction was synthesized by [W(CN)8]3− reacting with Mn(II) salt and hmpH in MeCN solution. The magnetic analyses show the antiferromagnetic coupling between metal ions and the influence of π–π stacking on the magnetic properties was investigated.Display Omitted
Keywords: Molecular magnetism; Octacyanotungstate; π–π stacking; Spin-polarization; Spin-delocalization;

Highly quantum efficiency trinuclear Eu3+ complex based on tris-diketonate ligand by Chaolong Yang; Jianxin Luo; Jianying Ma; Liyan Liang; Mangeng Lu (61-63).
A trinuclear Eu-complex based on tris-(β-diketonate) ligand was firstly designed and synthesized. The complex was characterized using IR, FAB-MS, 1H NMR, UV–visible, photoluminescence (PL) spectroscopy, element analysis (EA) and thermogravimetic analysis (TGA). Due to the contribution of two additional Eu3+ lumophors in the trinuclear Eu-complex, the complex exhibited much longer lifetime and higher quantum efficiency than mononuclear Eu-complex Eu(TTA)3phen. The CIE chromaticity coordinates (x = 0.66 and y = 0.33) showed a dominant wavelength of 613 nm, the color gamut achieved by this trinuclear Eu-complex was a 100% in the CIE color space. In addition, the trinuclear Eu-complex exhibited excellent thermal stability.Display OmittedA trinuclear Eu-complex based on tris-(β-diketonate) ligand was firstly designed and synthesized. Due to the contribution of additional two Eu3+ lumophors in the trinuclear Eu-complex, the complex exhibited much longer lifetime and higher quantum efficiency than mononuclear Eu-complex.►A trinuclear Eu-complex based on tris-(β-diketonate) ligand was firstly designed and synthesized. ►The complex exhibits much longer lifetime than mononuclear Eu-complex. ►The complex shows much higher quantum efficiency than mononuclear Eu-complex.
Keywords: Trinuclear europium complex; Luminescence property; Quantum efficiency; Lifetime;

A rare mercury coordination network containing left- and right-handed helical chains [HgL1Br2]n·nDMF (1) [L1  = 1,4-bis(3-pyridylaminomethyl)benzene] and dinuclear complex Hg2L2Br4(DMF)2] (2) [L2  = 1,4-bis(2-pyridylaminomethyl)benzene] have been synthesized. The thermal gravimetric and the solid-state luminescent properties of complexes were also investigated.A rare mercury coordination network containing left- and right-handed helical chains has been synthesized by the self-assembly of bis(pyridyl) ligands with longer flexible spacer and mercury bromide.Display Omitted
Keywords: Hg(II) complex; Helix structure; Bis(pyridyl) ligand; Luminescent property;

A new 3D fluorescent lanthanide-organic framework containing helical chains and zigzag layers from mixed carboxylate ligands by Zhi-Gang Gu; Jin-Hao Chen; Yue-Nan Chen; Yin Ying; Hui-Ming Peng; Hong-Yang Jia; Ming-Fang Wang; Shan-Shan Li; Yue-Peng Cai (68-71).
A new 3D lanthanide compound has been firstly synthesized employing 4,5-imidazoledicarboxylate and acetate mixed ligands. The structure contains zigzag layers, dinuclear praseodymium linkers and race-helical chains.Display Omitted
Keywords: Lanthanide-organic framework; Mixed carboxylate ligands; Zigzag layer; Race-helical chain; Fluorescence;

Two new chiral rare earth metal amidate complexes have been prepared. Both complexes are active catalysts for the polymerization of rac-lactide, leading to the isotactic-rich polylactides.Display Omitted
Keywords: Chiral amidate ligands; Yttrium complexes; Polymerization of lactide;

Anion-induced near-infrared (NIR) luminescent Zn2Nd and ZnNd complexes based on the pure Salen-type Schiff-base ligand by Weixu Feng; Yani Hui; Tao Wei; Xingqiang Lü; Jirong Song; Zhongning Chen; Shunsheng Zhao; Wai-Kwok Wong; Richard A. Jones (75-78).
With the Zn-Schiff-base [ZnL(CH 3 CN)] from the pure Salen-type Schiff-base ligand H 2 L (H 2 L  = N,N′-bis(salicylidene)phenylene-1,2-diamine) as the precursor, a hetero-trinuclear Zn2Nd complex [Zn2Nd(L)2(NO3)3(CH3CN)2] (1) and a hetero-binuclear ZnNd complex [ZnNd(L)2Cl(DMF)] (2) are obtained by the further reaction with Nd(NO3)3·6H2O or NdCl3·6H2O, respectively. The influence of structural differences of the two complexes on their photophysical properties shows the anionic inducement leads to the effective modulation of the NIR luminescent properties by the adjustment of the coordination sphere of the Nd3+ ions.A hetero-trinuclear Zn2Nd complex [Zn2Nd(L)2(NO3)3(CH3CN)2] (1) and a hetero-binuclear ZnNd complex [ZnNd(L)2Cl(DMF)] (2) are obtained from the further reaction of Nd(NO3)3·6H2O or NdCl3·6H2O with the Zn-Schiff-base [ZnL(CH 3 CN)] precursor from the pure Salen-type Schiff-base ligand H 2 L (H 2 L  = N,N′-bis(salicylidene)phenylene-1,2-diamine), respectively. The influence of structural differences of the two complexes on their photophysical properties shows the anionic inducement should be a potentially effective way to the modulation of the NIR luminescent properties by the adjustment of the coordination sphere of the Nd3+ ions.Display OmittedBased on the nuclearity of the d–f complexes of the pure Salen-type Schiff-base ligands by anion-inducement, the change of anions from NO3– to Cl– led to the formation of Zn2Nd (1) and ZnNd (2) complexes. Correlation of their molecular structures versus NIR luminescent properties showed the modulation of their NIR luminescence from anion-inducement should be relatively effective. ► Hetero-trinuclear and binuclear complexes. ► Effective modulation of NIR luminescence. ► Anion-inducement.
Keywords: Anionic inducement; Zn2Nd and ZnNd arrayed Schiff-base complexes; Sensitization and energy transfer; Modulation of NIR luminescence;

The synthesis, spectrophotometric and surfactant properties of a novel amphiphilic cobalt cage metallosurfactant with an aza-oxa crown ether spacer and dodecyl hydrocarbon tail are reported. Surface pressure isotherms with Group I and Group II metal solution subphases indicate increasing interaction of the crown moiety with Ca2+, Na+, K+, Li+/Ba2+ and Mg2+ ions in that order, with mean molecular areas of the effective head group at the surface ranging from 141 Å2 to 219 Å2. The critical micelle concentrations determined by surface tension measurements of the unmetallated ligand and the metallosurfactant are 1.98 mM and 0.66 mM respectively. Wormlike micelles and vesicles are observed with atomic force microscopy after multilayer Langmuir Blodgett film deposition on a glass substrate.A novel cobalt cage aza-crown amphiphile is described and its mean molecular area in a compressed monolayer estimated from Langmuir isotherms. In the presence of alkali and alkali earth metals, preferential coordination to magnesium ions and large solvated ions by a crown subunit is observed at the interfacial zone.Display Omitted
Keywords: Diamsar; Metallosurfactant; Amphiphile; Aza-crown spacer; Langmuir isotherms; Wormlike micelles;

Self-assembly of cyclometallated Pd(II) compounds directed by C–H⋅⋅⋅π interactions: A structural evidence for metalloaromaticity in a cyclopalladated ring by Anderson M. Santana; Janaína G. Ferreira; Antonio C. Moro; Sahra C. Lemos; Antonio E. Mauro; Adelino V.G. Netto; Regina C.G. Frem; Regina H.A. Santos (83-86).
Structural studies on the two binuclear cyclometallated compounds [Pd(C 2 ,N-bzan)(μ-N3)]2 (1) and [Pd(C 2 ,N-bzan)(μ-Pz)]2 (2) (bzan = N-benzylideneaniline) have been carried out in this work. In both compounds, C–H⋅⋅⋅π interactions play an important role in the molecular self-assembly. In complex 1, ortho-CH bonds from bzan moiety interact with the cyclopalladated ring at a distance of Cbzan⋅⋅⋅Cg 3.448(6) Å, providing a new structural evidence for the metalloaromaticity of the cyclometallated ring.Structural studies on the cyclometallated [Pd(C 2 ,N-bzan)(μ-N3)]2 (1) and [Pd(C 2 ,N-bzan)(μ-Pz)]2 (2) (bzan = N-benzylideneaniline, Pz = pyrazolato) revealed that C–H⋅⋅⋅π interactions are responsible for the stabilization of their crystal structures. In complex 1, ortho-CH bonds interact with the metal chelate ring, providing a new structural evidence for the metalloaromaticity of a cyclometallated ring.Display Omitted
Keywords: Supramolecular chemistry; C–H⋅⋅⋅π interactions; Cyclopalladated; Metalloaromaticity;

The reaction of Zn(NO3)2∙3(H2O) with trans-aconitic acid (H3L), in presence of chelating 1,10-phenanthroline, leads to the formation of a dinuclear unit {[Zn(HL)(phen)(H2O)]∙3(H2O)}2. The lattice water molecules are assembled as a centrosymmetric hexamer. The crystal structure, thermal studies, theoretical calculations, and the factors that stabilize this water hexamer are presented.A new type of binodal network has been constructed by a zinc(II) trans-aconitate dimer and a water hexamer through H-bonds.Display Omitted
Keywords: Hexameric water cluster; Zinc(II); 3D metal-supramolecular architecture; H-bond; Crystal structure;

Enantiopure trinuclear lanthanide(III) complexes: Cooperative formation of Ln33-OH)2 core within the macrocycle by Marta Paluch; Katarzyna Ślepokura; Tadeusz Lis; Jerzy Lisowski (92-95).
The large trioxahexaaza chiral macrocyclic amine L binds three lanthanide(III) ions (Sm(III), Eu(III) and Tm(III)) in such a way that the Ln(III) ions are bridged by the phenolate oxygen atoms of the macrocycle and additional hydroxo bridges. The formation of symmetrical trinuclear complexes is confirmed by 1H NMR, ESI-MS and elemental analyses. X-ray crystal data for the Eu(III) complex reveal the presence of the Ln33-OH)2 cluster in the centre of the macrocycle. On the other hand, the larger La(III) or Pr(III) lanthanide ions form dinuclear complexes with the macrocycle L under similar conditions. The titration of the macrocycle L with europium(III) nitrate and sodium hydroxide solutions indicates formation of mononuclear and trinuclear species, while no substantial amount of dinuclear complexes are observed. The formation of the Ln33-OH)2 core in the trinuclear complexes is cooperative, i.e. the binding of the third Ln(III) ion by the macrocycle L is stronger than the binding of the second Ln(III) ion.Novel trinuclear lanthanide(III) (Sm(III), Eu(III) and Tm(III)) complexes of a large chiral 3 + 3 macrocyclic amine L have been isolated and characterized. The crystal structure of the Eu(III) complex reveals the presence of the Ln33-OH)2 cluster in the centre of the macrocycle.Display Omitted
Keywords: Lanthanides; Macrocycles; Trinuclear complexes; Chiral complexes; Cooperativity; Crystal structure;

Alkyl carbonates are split by two subsequent photochemical steps using CuITp* (Tp* = hydrotris (3,5-dimethyl-1-pyrazolyl)borate) as photoredox agent: (1) C O O R 2 + 2 H 2 O + 2 C u I T p * → C O + T p * C u I I μ − O H 2 C u I I T p * + 2 R O H (2) T p * C u I I μ − O H 2 C u I I T p * → 2 C u I T p * + H 2 O 2 O 2 . It is suggested that this scheme provides a good model for the cleavage of CO2 to CO and oxygen representing a rather simple type of artificial photosynthesis. Photoreactions 1 and 2 correspond to photosystems I and II of natural photosynthesis.The stable molecule carbon dioxide can be photo cleaved by intramolecular electron transfer between suitable redox-active metal centers such as carbonate instead of carbon dioxide. After CT excitation the formation of stable products is determined by the availability of appropriate oxidation states at the metal centers.Display Omitted► Carbon dioxide splitting generating carbohydrates and oxygen takes place in nature. ► Our artificial photosynthesis was carried out by cleaving CO2 to CO and O2. ► We report the splitting of alkyl carbonates photocatalyzed by copper complexes. ► These observations form a reliable basis for achieving our final goal in the future.
Keywords: Coordination chemistry; Dialkyl carbonates; Copper; Photocatalysis; Artificial photosynthesis;

The bipodal ligand 3,3,3′,3′-tetraethyl-1,1′-isophthaloyl-bis(selenourea) (H2L1) forms a 2:2 copper(II) complex [Cu2(L1)2] , the crystal and molecular structure and EPR spectrum of which are reported. Treatment of [Cu2(L1)2] with excess pyridine results in the formation of a novel (bis-N-acylureato)copper(II) 1:2 pyridine adduct [Cu2(L2)2(py)2], characterized by single crystal X-ray diffraction and EPR spectroscopy, as a consequence of facile Se replacement by O presumably due to hydrolysis of water present in the mixture. The latter complex forms a one-dimensional supramolecular architecture in the solid state, stabilized via π-stacking interactions between alternate Cu-coordinated pyridine molecules.Display OmittedThe bipodal ligand 3,3,3′,3′-tetraethyl-1,1′-isophthaloyl-bis(selenourea) (H2L1) forms a 2:2 copper(II) complex [Cu2(L1)2] , the crystal and molecular structure and EPR spectrum of which are reported. Treatment of [Cu2(L1)2] with excess pyridine results in the formation of a novel (bis-N-acylureato)copper(II) 1:2 pyridine adduct [Cu2(L2)2(py)2] as a consequence of facile Se replacement by O due to hydrolysis of water present in the reaction mixture.
Keywords: Crystal structures of {(bis-N-isophthaloyl-selenoureato)copper(II)}2; {(bis-N-isophthaloyl-ureato)-copper(II)}2•2pyridine; EPR spectroscopy; Se by O atom exchange;

A new compound based on Preyssler-type P5W30 anion modified by CoII and flexible bis(benzimidazole) ligand by Xiuli Wang; Jin Li; Aixiang Tian; Hongyan Lin; Guocheng Liu; Hailiang Hu (103-106).
Display Omitted
Keywords: Polyoxometalates; Preyssler-type anions; Cobalt cation; Benzimidazole; Electrochemical property;

Display Omitted►Design of bimetallic oxides using a dipodal nitrogen chelate. ►Structure of a 2-D copper-molybdate with the {Mo8O26(H2O)2}4-building block. ►Structure of a 3-D copper-molybdate with {Mo8O26}4- and {MoO4}2- building units.
Keywords: Copper molybdate coordination polymers; Octamolybdate cluster building blocks; Organonitrogen dipodal ligands; Hydrothermal synthesis;

The oxidative addition of cyclopropylmethyl or cyclobutylmethyl bromide to [PtMe2(bipy)], 1, bipy=2,2′-bipyridine, gave the products of trans-oxidative addition [PtBrMe2(CH2-c-C3H5)(bipy)], 2, or [PtBrMe2(CH2-c-C4H7)(bipy)], 3. These compounds are thermally stable but the complex [Pt(O2CCF3)Me2(CH2-c-C3H5)(bipy)] rearranges on heating to give the ring-opened complex [Pt(O2CCF3)Me2(CH2CH2CH=CH2)(bipy)]. Factors affecting the reactivity towards ring-opening are discussed.The cycloalkylmethylplatinum(IV) complexes [PtBrMe2(CH2-c-C3H5)(bipy)] and [PtBrMe2(CH2-c-C4H7)(bipy)] are thermally stable but [Pt(O2CCF3)Me2(CH2-c-C3H5)(bipy)] rearranges on heating to give the butenyl complex [Pt(O2CCF3)Me2(CH2CH2CH=CH2)(bipy)]. Factors affecting the reactivity towards ring-opening are discussed.Display Omitted►Cyclopropylmethyl and cyclobutylmethyl complexes of platinum(IV) are prepared by oxidative addition. ►These complexes are stable to ring-opening under mild conditions. ►The cyclopropylmethyl complex rearranges to the 3-butenyl isomer if a coordination site is opened up. ►The reasons for unusual stability of the ring compounds is elucidated.
Keywords: Platinum; Cyclopropyl; Butenyl; Cyclobutyl;

The first protonated hexatantalate, [H2Ta6O19]6−, has been synthesized and structurally characterized. X-ray diffraction analysis revealed that the protons are selectively attached to the O atoms that bridge two Ta atoms. The overall structure of the [H2Ta6O19]6− anion is virtually identical to that predicted by a DFT calculation.The first protonated hexatantalate, [H2Ta6O19]6-, has been synthesized and structurally characterized. X-Ray diffraction analysis revealed that the protons are selectively attached to the O atoms that bridge two Ta atoms. The overall structure of the [H2Ta6O19]6- anion is virtually identical to that predicted by a DFT calculation.Display Omitted
Keywords: Molecular oxide; Polytantalate; Lindqvist anion; Protonation;

A new Keggin POM-based compound exhibits 2D wave-like metal–organic layers, which are further linked by Keggin anions to construct a 3D framework containing two kinds of quadrate channels. The void left by channels induces an interesting two-fold interpenetrating structure.Display Omitted
Keywords: Keggin polyoxometalate; Hydrothermal synthesis; Flexible bis(triazole) ligand; Two-fold interpenetrating structure;

Trinuclear copper(I) and silver(I) acetylide complexes containing carboxylate group, [Cu3(μ-dppm)331-C ≡ CCOO)(μ3-OCH3)] and [Ag3(μ-dppm)331-C ≡ CCOO)(μ3-Cl)], have been synthesized and their photophysical properties investigated (dppm = bis(diphenylphosphino)methane). Their X-ray crystal structures have been determined.Luminescent trinuclear copper(I) and silver(I) acetylide complexes containing carboxylate group have been synthesized and characterized. Their photophysical properties were studied.Display Omitted► Trinuclear copper(I) and silver(I) acetylide complexes with carboxylate group have been synthesized. ► Weak copper⋅⋅⋅copper or silver⋅⋅⋅silver interactions exist in these metal acetylide complexes. ► These metal acetylide complexes show intense luminescence in the solid state at 298 K.
Keywords: Acetylide; Carboxylate; Copper; Luminescence; Silver;

The first pentanuclear heterobimetallic coordination cation with CeIII, CeIV and MnII by Mohammad Mahdi Najafpour; Bojan Kozlevčar; Vickie McKee; Zvonko Jagličić; Marko Jagodič (125-127).
[Mn2(μ-dipic)2(H2O)6]·2H2dipic (dipic = dipicolinate) reacts with (NH4)2[Ce(NO3)6] to produce the pentanuclear coordination species in [MnCe4(μ-dipic)6(H2O)20][Ce(dipic)3]2·11H2O (1). The coordination anion [Ce(dipic)]2− is formed by three tridentate O,N,O dipicolinate(2−) anionic ligands around the metal CeIV cation. The same pattern is found for two CeIV in the pentanuclear CeIII/CeIV/MnII/CeIV/CeIII chain-like coordination cation [MnCe4(μ-dipic)6(H2O)20]4+. The CeIV(dipic)3 moieties in the cation coordinatively bridge the terminal CeIII(H2O)8 with the central MnII(H2O)4 units. Each manganese(II) ion is thus 6-coordinated and each cerium(III, IV) ion is 9-coordinated. During the synthesis of 1, the gaseous dioxygen is evolved, due to water oxidation that is attributed to the presence of Ce and Mn in different oxidation states.The first pentanuclear heterobimetallic coordination cation with Ce(III), Ce(IV) and Mn(II): [Mn2(μ-dipic)2(H2O)6]·2H2dipic (dipic = dipicolinate) reacts with (NH4)2[Ce(NO3)6] to produce the pentanuclear coordination species in [MnCe4(μ-dipic)6(H2O)20][Ce(dipic)3]2·11H2O.Display Omitted
Keywords: 2,6-Pyridinedicarboxylate; Cerium; Manganese; Crystal structure; Water oxidation;

The mononuclear copper(II) complexes with 3rd generation quinolone drug sparfloxacin (SPFH) in the presence of nitrogen donor heterocyclic ligands (A1  = 2,9-dimethyl-1,10-phenanthroline, A2  = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, A3  = 4,5-diazafluoren-9-one, A4  = 1,10-phenanthroline-5,6-dione, and A5  = 5-nitro-1,10-phenanthroline) have been prepared and characterized. An antimicrobial efficiency of the complexes has been tested on five different microorganisms and shows diverse biological activity. Absorption titration, thermal denaturation and viscosity measurement study showed that all complexes binds to DNA by an intercalative mode. The DNA cleavage ability of the complexes was determined using gel electrophoresis. Complexes exhibit SOD-like activity with their IC50 values ranging from 0.512 to 1.225 μM.Square pyramidal copper(II) complexes have been synthesized using sparfloxacin and nitrogen donor heterocyclic ligands. Their antibacterial, DNA interaction and SOD-like activity have also been evaluated.Display Omitted
Keywords: Sparfloxacin; Copper(II) complexes; MIC; Interaction with DNA; SOD mimic;

Nine new organotin complexes, namely [SnR2XY(BtzH)2] (1: R = Me, X = Y = Cl, 2: R = Me, X = Y = Br, 3: R =  n Bu, X = Cl, Y = OH; 4: R = Ph, X = Y = Cl; 5a: R = Me, X = Y = NO3; 5b: R = Me, X = Y = ClO4) and [SnR2X2(5-NO2indH)2] (6: R = Me, X = Cl; 7: R =  n Bu, X = Cl; 8: R = Me, X = 5-NO2ind) were obtained by reaction of SnR2X2 with BtzH (1,2,3-benzotriazole) and 5-NO2indH (5-nitroindazole). These compounds were characterized by IR, NMR and ESI MS, and 1 is shown by a single crystal X-ray study to comprise mononuclear centrosymmetric molecules, all pairs of ligands being mutually opposed in a quasi-octahedral coordination sphere. Sn–Cl, C, N are 2.5700(5), 2.108(2), 2.357(2)Å. A new triclinic ( P 1 ¯ ) polymorph of the binuclear [{ t Bu2ClSn(μ-OH)}2], 9 is also described (cf. the earlier monoclinic (P21/c)). The unit cell contents comprise a pair of centrosymmetric dimers: Sn–O are 2.042(4)–2.215(4), Sn–Cl 2.489(2), 2.491(2), Sn–C 2.166(6)–2.203(7) Å, O–Sn–O 68.4(2) (x2), and Sn–O–Sn 111.6(2)° (x2).Novel organotin complexes [SnR2XY(BtzH)2] and [SnR2X2(5-NO2indH)2] obtained by reaction of SnR2X2 with 1,2,3-benzotriazole and 5-nitroindazole have been characterized by IR, NMR, TGA, X-ray and ESI MS.Display Omitted► First benzotriazoleorganotin(IV) structurally characterized. ► Combined techniques to understand solid and solution states. ► Reactivity of organotin adducts toward silver salts.
Keywords: Benzotriazole; Indazole; Organotin(IV); Crystal structure; ESI MS;

New homochiral coordination polymers have been synthesized by a dual-ligand synthetic approach under hydro/solvothermal conditions. Their structures vary from an infinite 1D chain through 2D nanoporous layer to a 3D network.Display Omitted► The use of bis(imidazole) molecules with d-camphoric acid as the cross-linkers results in the formation of three new homochiral coordination polymers with various framework structures under hydro/solvothermal conditions.
Keywords: Crystal structure; Coordination polymer; Homochiral network; Camphorate; Photoluminescence;

The syntheses, X-ray crystal structures and topological analyses of a three-dimensional coordination polymer complex, {Cd(BTC)Na(H2O)3}n 1 (BTC3−  = 1,3,5-benzenetricarboxylic anion), are reported. Complex 1 features a hetero-metallic framework built by alkali metal (sodium) and d10 metal (cadmium) with organic BTC. From a topological point of view, the whole structure can be considered as an anionic rtl (rutile) net constructed from Cd2+ and BTC3− decorated by polymeric cationic chains of [Na(H2O)3]n +.A three-dimensional coordination polymer complex, {Cd(BTC)Na(H2O)3}n 1 (BTC3−  = 1,3,5-benzenetricarboxylic anion), is reported. Complex 1 features a hetero-metallic framework built by alkali metal (sodium) and d10 metal (cadmium) with organic BTC. From a topological point of view, the whole structure can be considered as an anionic rtl (rutile) net constructed from Cd2+ and BTC3− decorated by polymeric cationic chains of [Na(H2O)3]n +.Display Omitted► A hetero-metallic framework built by alkali metal (sodium) and d10 metal (cadmium) with organic BTC. ► The whole structure can be considered as an anionic rtl (rutile) net constructed from Cd2+ and BTC3- decorated by polymeric cationic chains of [Na(H2O)3]n +. ► Complex 1 exhibits luminescent emission maxima at 412 nm.
Keywords: X-ray crystal structure; Hetero-metallic; Topological analysis; Rutile;

Synthesis, structure and properties of novel 3-D porous lanthanide-3, 4′, 5-azobenzenetricarboxylate frameworks by Lingling Zhang; Cuiying Lu; Sanping Chen; Fushan Yu; Xia Li; Jinting Tan; Xuwu Yang (143-145).
{[Gd2(ABTC)2(DMF)2(H2O)2]·DMF·H2O}n is a [Ln2(COO)6] dinuclear group, which serves as octahedral secondary building units (SBUs) to produce a novel 3-D porous framework. Moreover, it could be anticipated to be potential antiferromagnetic materials.Display Omitted►The complex is the octahedral SBUs containing chelate-bridging carboxylate groups. ►The complex is first example to construct noninterpenerative LMOF with the octahedral SBUs. ►The complex presents antiferromagnetic behavior.
Keywords: Lanthanide; Porous metal-organic framework; Magnetic property;

A novel diamagnetic ruthenium nitrosyl complex having {RuNO}6 moiety was synthesized and characterized spectroscopically. It has been found out that the coordinated NO was photolabile. Photolability of the coordinated NO was examined under visible as well as UV light and photolabile NO was transferred to reduced myoglobin.Display Omitted►Ruthenium nitrosyl complex. ►Photorelease of coordinated NO. ►NO transfer to reduced myoglobin.
Keywords: Ruthenium nitrosyl complex; Nitric oxide; Photolabile; Myoglobin trapping 1H and 31P NMR;

Display Omitted
Keywords: Zinc phosphite; Structure and characterization; Inorganic framework; Knoevenagel condensation; Catalyzed reactions;

A series of new RuII-Schiff base complexes of containing Ph3P has been prepared and characterized. The complexes have been used as catalysts for the oxidation of alcohols in [EMIM]Cl ionic liquid–NaOCl system. Higher catalytic activity was found for RuL1. A plausible mechanism has been proposed.Ruthenium (II)-Schiff base complexes with triphenylphosphine were effective in the oxidation of primary and secondary alcohols in ethyl–methyl–imidazolium ionic liquid medium in the presence of NaOCl.Display Omitted►Short reaction time of 30 min. ►An approach towards green synthesis. ►A variety of alcohols were selectively oxidized to their corresponding carbonyl compounds.
Keywords: Ru complexes; Catalytic oxidation; Ionic liquid; NaOCl;

Synthesis, crystal structure and photoluminescence of iridium (III) coumarin complexes by Tianzhi Yu; Sidan Yang; Jing Meng; Yuling Zhao; Hui Zhang; Duowang Fan; Xiaoqian Han; Zaiman Liu (159-161).
Two novel iridium organometallic compounds, Ir(III)bis(3-(pyridin-2-yl)coumarinato N,C4)(thenoyltrifluoroacetonate) and Ir(III) bis(3-(pyridin-2-yl)coumarinato N,C4)(acetylacetonate) [Ir(L)2(TTA) and Ir(L)2(acac)], were synthesized and characterized by elemental analysis, 1 H NMR, FT-IR and UV–vis absorption spectra. X-ray crystallography demonstrated that Ir atom is six coordinated in Ir(III)bis(3-(pyridin-2-yl)coumarinato N,C4)(thenoyltrifluoroacetonate). Both the iridium organometallic compounds emit intense green emissions, indicating that they are useful for the fabrication of organic light-emitting diodes.Graphical abstractTwo novel iridium complexes containing coumarin derivative as a cyclometalated ligand, Ir(L)2(TTA) and Ir(L)2(acac), were synthesized and characterized. Among them, Ir(L)2(TTA) has been structurally characterized by X-ray crystallography, in which Ir atom is six coordinated. The complexes exhibit strong green emissions on irradiation by UV light.Display Omitted► Highly efficient phosphorescent Ir (III) complexes have been reported widely, but phosphorescent Ir (III) complexes containing coumarin derivatives as cyclometalated ligands were reported rarely. In this communication, two novel iridium complexes containing coumarin derivative as cyclometalated ligand and β- diketones as the ancillary ligands were synthesized and characterized. ► The crystal structure of Ir(III)bis(3-(pyridin-2-yl)coumarinato N,C4) (thenoyltrifluoroacetonate) was firstly reported. ► The complexes reported exhibit intense green emissions, which are desirable for examples in OLED applications.
Keywords: Synthesis; Iridium (III) complexes; Coumarin derivative; Photoluminescence;

A unique, rigid porous coordination polymer with 1,4,5-triazanaphthalene and mixed-valence Cu as the bridging metal by Gerard A. van Albada; Mohamed Ghazzali; Khalid Al-Farhan; Ilpo Mutikainen; Jan Reedijk (162-165).
A novel mixed-valence Cu(I)/Cu(II) compound with the bridging ligand 1,4,5-triazanaphthalene (tan) is reported, having the overall formula [Cu2(tan)4](ClO4)3. The synthesis, X-ray crystal structure and preliminary spectroscopic properties are presented. The coordination of Cu(I) is tetrahedral, and that of Cu(II) is square planar. The packing of the units generates a 3D network with spaces in the cavities, available for the counter anions and accessible for small solvent molecules.A novel mixed-valence porous Cu compound consisting of 1,4,5-triazanaphthalene bridging ligands is described.Display Omitted
Keywords: Copper; Metal-organic framework; Mixed-valence;

Syntheses, crystal structures, magnetic properties of two lanthanide-nitronyl nitroxide complexes (LnIII  = GdШ, PrШ) by Chen-Xi Zhang; Na-Na Sun; Xiang-Yu Zhao; Yu-Ying Zhang; Yan-Ling Guo (166-168).
Two complexes based on rare-earth-radical of formula {Ln(hfac)3[NITPh(OCH3)3]2} (Ln = Gd (1), Pr(2)); hfac = hexafluoroacetylacetonate; NITPh(OCH3)3  = 2-(3′,4′,5′-trimethoxyphenyl)-4,4,5,5-tetramethylimidazoline -1-oxyl-3-oxide) have been synthesized and characterized by single-crystal X-ray diffraction. The single-crystal structures show that two complexes have similar structures, in which the metal ions are eight-coordinated in slightly distorted dodecahedron geometry. Two oxygen atoms of the N–O group from nitronyl nitroxide radicals and six oxygen atoms from three different hfac anions are coordinated to the metal ions. The magnetic studies show that the spin coupling between the Gd(III) ion and the radicals in the complex 1 is ferromagnetic (J  = 1.46 cm−1), while complex 2 exhibits antiferromagnetic interactions (zJ′ = −0.21 cm−1) between Pr(III) ion and radicals.Two complexes based on rare-earth-radical have been synthesized and characterized by single-crystal X-ray diffraction. These complexes have similar structures, in which the metal ions are eight-coordinated in slightly distorted dodecahedron geometry. The magnetic studies show that the spin coupling between the Gd(III) ion and the radicals in the complex 1 is ferromagnetic, while complex 2 exhibits antiferromagnetic interactions between Pr(III) ion and radicals.Display Omitted► Synthesize two rare-earth metal complexes based on nitronyl nitroxide radicals. ► Two complexes have eight-coordinated dodecahedron geometry. ► Weak ferromagnetic coupling exists between Gd(III) ion and radical. ► Weak antiferromagnetic interaction exists between the Pr(III) ion and radical.
Keywords: Crystal structure; Nitronyl nitroxide metal complexes; Magnetism;

Trimethylphosphite stabilized N-silver(I) succinimide complexes as CVD precursors by Xian Tao; Yu-Long Wang; Ke-Cheng Shen; Ying-Zhong Shen (169-171).
The preparation of [(MeO)3P n ·AgNC4H4O2] (n  = 1, 2a; n  = 2, 2b) is described. The molecular structure of 2a was determined by using X-ray single crystal analysis. Complex 2b was tested as Metal Organic Chemical Vapor Deposition (MOCVD) precursor in the deposition of silver for the first time. The thin films obtained were characterized using scanning electron microscopy (SEM) and energy-dispersion X-ray analysis (EDX). SEM and EDX studies show that the dense and homogeneous silver films could be obtained.The preparation of [(MeO)3P n ⋅ AgNC4H4O2] (n  = 1, 2a; n  = 2, 2b) is described. The molecular structure of 2a has an Ag–O bond which is different with similar complexes. Complex 2b was tested as Metal Organic Chemical Vapor Deposition (MOCVD) precursor in the deposition of silver for the first time. SEM and EDX studies show that closed and homogeneous silver films could be obtained.Display Omitted
Keywords: Silver; Succinimide; Precursor; MOCVD; Deposition; Trimethylphosphite;

Two three-dimensional pillar-layer AgI-frameworks with helical arrays containing hexamine by Peng Guo; Jing Wang; Gang Wang; Shen-jie Li; Wen-zhi Huang; Yu-han Lin; Guo-hai Xu; Dao-cheng Pan (172-175).
Two three-dimensional pillar-layer AgI-frameworks with helical arrays have been synthesized under room temperature. Compound I, {[Ag2 (H2O) (L2)2L1].H2O}n(L1 = hexamethylenetetramine, H1L2 = 3-Pyridinesulfonic acid), is constructed from two-dimensional (6,3) layers which are braced by helical arrays; Compound II, {[Ag3(L1)2(L3)].6H2O}n (H3L3 = citric acid), is created by two-dimensional layers which are made up of the mix-helical arrays and further pillared by L3 anions and Ag ions. Compound I and compound II have been characterized by single-crystal X-ray structure determination, powder X-ray diffraction, IR and TGA. Also, the water and methanol adsorption isotherms for Compound II have been studied.A three-dimensional AgI-framework, {[Ag2 (H2O) (L2)2L1].H2O}n (Compound I)(L1 = hexamethylenetetramine, HL2 = 3-Pyridinesulfonic acid)with a (3, 5)-connected topology in which the two-dimensional (6,3) layer is braced by the right-handed helices (P) and left-handed ones (M), has been synthesized by the conventional evaporation method while compound II, {[Ag3(L1)2(L3)].6H2O}n (H3L3 = citric acid), with a (3, 4)-connected topology, is constructed from a 2D (6, 3) layer which is made up of mix-helical arrays and further pillared by the L3 ligands and Ag ions.Display Omitted► Helical structures are found in the three-dimension AgI-framework. ► Two types of 3D pillar-layer with helical structures are constructed. ► Boat conformation (H2O)6 clusters accommodate in the three-dimension framework.
Keywords: AgI-framework; Helical structures; Metal organic frameworks; Pillar-layer structures;

Two heterotrimetallic compounds, [Cu(en)2Li(H2O)][Fe(CN)6] and [Cu(en)2Li(H2O)][Co(CN)6] (en = ethylenediamine), were synthesized and characterized. They are isostructural and crystallize in the orthorhombic space group Pbca at 293 K. The structures of the two compounds are composed of one-dimensional zigzag Fe/Co–C≡N–Cu chains linked by Li(I) ions into three-dimensional frameworks. Magnetic study of [Cu(en)2Li(H2O)][Fe(CN)6] reveals a weak magnetic interaction in the compound.Two heterotrimetallic compounds, [Cu(en)2Li(H2O)][Fe(CN)6] and [Cu(en)2Li(H2O)][Co(CN)6] (en = ethylenediamine), were synthesized and characterized. They are isostructural and crystallize in the orthorhombic space group Pbca at 293 K. The structures of the two compounds are composed of one-dimensional zigzag Fe/Co−C≡N−Cu chains linked by Li(I) ions into three-dimensional frameworks. Magnetic study of [Cu(en)2Li(H2O)][Fe(CN)6] reveals a weak magnetic interaction in the compound.Display Omitted► Heterotrimetallic compounds [Cu(en)2Li(H2O)][M(CN)6] (M = Fe(III) or Co(III); en = ethylenediamine) are composed of one-dimensional zigzag M − C ≡ N − Cu chains linked by Li(I) ions into three-dimensional frameworks. ► Magnetic measurements of [Cu(en)2Li(H2O)][Fe(CN)6] reveal a weak magnetic interaction. ► This study shows the possibility of using a third diamagnetic metal ion to control structures and magnetic properties of Cu(II)-Fe(III)-cyanide compounds.
Keywords: Hexacyanometallate; Copper; Crystal structure; Zigzag chain; Magnetic property;

Novel mononuclear mixed ligand Ce(III) pivalate with protonated cationic form of monoethanolamine as ancillary ligand by Natalia P. Kuzmina; Irina A. Martynova; Dmitry M. Tsymbarenko; Konstantin A. Lyssenko (180-183).
The mononuclear mixed ligand Ce(III) pivalate with protonated cationic form of monoethanolamine (MEA) as ancillary ligand is reported. Crystal structure consists of mononuclear complex anions [Ce(Piv)5(HOCH2CH2NH3)] (HPiv–2,2-dimethylpropionic (pivalic) acid) and cations [HOCH2CH2NH3]+ connected by hydrogen bonds into hexagonal layers packed over α-graphite motif. Central cerium ion coordinates six oxygen atoms of three bidentate chelate Piv ligands, two O atoms of two monodentate pivalate ligands and one — of MEA in N-protonated cationic form. Five tert-butyl groups of pivalate ligands shield cerium(III) ion that facilitates coordination of ancillary ligand with positive charge on its peripheral part.A novel mononuclear mixed ligand Ce(III) pivalate with protonated cationic form of monoethanolamine (MEA) as ancillary ligand is reported. Crystal structure consists of mononuclear complex anions [Ce(Piv)5(HOCH2CH2NH3)] (HPiv–2,2-dimethylpropionic (pivalic) acid) and cations [HOCH2CH2NH3]+ connected by hydrogen bonds into hexagonal layers packed over α-graphite motif.Display Omitted► Crystal structure of mononuclear Ce(III) pivalate with MEA have been determined. ► Protonated MEA ions act either as inner-sphere ligands or as external cations. ► In complex anion Ce(III) coordinates five pivalate ligands and protonated MEA cation. ► Complex anions and external cations are H-bonded into layers with α-graphite motif.
Keywords: Cerium (III); Mononuclear; Pivalate; Monoethanolamine; Crystal structure;

Ester catalytic hydrolysis by a tridentate N,N′,N″-copper bridged cyclodextrin dimer by Si-Ping Tang; Sha Chen; Guang-Fei Wu; Huo-Yan Chen; Zong-Wan Mao; Liang-Nian Ji (184-188).
A new pyridine bridged cyclodextrin dimer mono-copper complex (CuL) was synthesized and characterized. The hydrolysis of carboxylic acid esters, bis(4-nitrophenyl)carbonate (BNPC) and 4-nitrophenyl acetate (NA), and phosphate ester, a DNA model bis(4-nitrophenyl)phosphate (BNPP), promoted by CuL has been investigated. The resulting hydrolysis rate constants showed that CuL had a very high rate of catalysis for BNPC hydrolysis, yielding a 2.73 × 103-fold rate enhancement over uncatalyzed hydrolysis at pH 7.00, compared to only a 78.2-fold rate enhancement for NA hydrolysis. The initial first-order rate constant of catalytic hydrolysis for BNPP was 1.01 × 10−7  s−1 at pH 8.5, 35 °C and 0.1 mM catalyst concentration, about 1260-fold acceleration over uncatalyzed hydrolysis. The second rate constant k BNPP of BNPP hydrolysis promoted by CuL was found to be 5.94 × 10−4  M−1  s−1.A new pyridine bridged cyclodextrin dimer copper complex (CuL) was prepared, characterized and demonstrated as a potent catalyst for ester hydrolysis. The cooperative binding action of both hydrophobic cavities with substrate plays an important role on ester cleavage.Display Omitted► Copper complex based on cyclodextrin dimer as ester hydrolysis catalyst. ► The copper complex exhibited high rate for diesters hydrolysis. ► The cooperation of two cavities of CDs plays an important role on ester cleavage.
Keywords: Cyclodextrin dimer; Hydrolysis; Kinetics; Ester; Copper complex;

A new series of air-stable Co(II) complexes, [bpmaL1]CoCl2 (1a), [bpmaL2]CoCl2 (2a), [bpmaL3]CoCl2 (3a), and [bpmaL4]CoCl2 (4a), where, for example, [bpmaL1 =  N,N-bis{(1-pyrazolyl)methyl}aniline], has been synthesized. X-ray crystallography of 2a indicated that it has a dipper-type structure in which the aniline moiety plays the role of the handle with a tetrahedral cobalt located at the edge with an eight-membered chelate ring formation. However, there is no indication that the metal is coordinated to the nitrogen of the aniline group. Moreover, complexes showed the highest catalytic activity in the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) with an activity of 1.14 × 106  g PMMA/mol-Co·h at 60 °C and syndiotacticity of PMMA, characterized by 13  C NMR spectroscopy, which value was ca. 0.57.A new series of air-stable Co(II) complexes, [bpmaL1]CoCl2 (1a), [bpmaL2]CoCl2 (2a), [bpmaL3]CoCl2 (3a), and [bpmaL4]CoCl2 (4a) have been synthesized and specifically, complex 2a was structurally characterized by X-ray crystallography. Complexes were evaluated as a catalyst for the polymerization of methyl methacrylate (MMA), the activity of MMA polymerization increased sharply with increasing temperature, the conversion reached up to 70% at 60 °C with narrow PDI (Mw/Mn) ca. 2. In addition, syndiotacticity of PMMA characterized by 13  C NMR spectroscopy, in which the value was ca. 0.57.Display Omitted
Keywords: N,N-bis(1-H-Pyrazole-1-yl); Tetrahedral Co (II) complex; Methyl methacrylate; PMMA;

The title compound was proposed as a paramagnetic host, and its chelation ability was confirmed by inclusion of a size-matching lanthanum(III) ion. The anti-configuration of the free ligand was changed to the syn configuration in the complex. The antiferromagnetic coupling was enhanced after complexation. In addition to the change of the intramolecular magnetic coupling, a superexchange mechanism is also assumed across the nitroxide–lanthanum(III)–nitroxide structure.The title compound was proposed as a paramagnetic host, and its chelation ability was confirmed by inclusion of a size-matching lanthanum(III) ion. The antiferromagnetic coupling was enhanced after complexation. Display Omitted►A novel paramagnetic host has been developed. ►Stable under ambient conditions. ►Host-guest complexation with configuration change. ►Full structural and magnetic characterization.
Keywords: Supramolecular chemistry; Magnetic property; Organic free radical; Lanthanum; Bipyridine;

Display Omitted
Keywords: Hydrothermal synthesis; Lead; Topology; Helix; Incomplete cubane-like cluster;

Adjustment of coordination environment of Ln3+ ions to modulate near-infrared luminescent properties of Ln3+ complexes by Yani Hui; Weixu Feng; Tao Wei; Xingqiang Lü; Jirong Song; Shunsheng Zhao; Wai-Kwok Wong; Richard A. Jones (200-204).
With the Zn-Schiff-base [ZnL(Py)] from the pure Salen-type Schiff-base ligand H2L (H2L = N,N′-bis(salicylidene)ethylene-1,2-diamine) as the precursor, a series of hetero-trinuclear Zn2Ln complexes [Zn2Ln(L)2(NO3)2(SCN)(Py)2] (Ln = Nd, 1; Ln = Yb, 2; Ln = Er, 3 and Ln = Gd, 4) are obtained by the further reaction with Ln(NO3)3·6H2O and KSCN on the condition of stoichiometry control, respectively. The influence of molecular structures on the photophysical properties shows their NIR luminescent properties are hypersensitive to the composition and symmetry of the coordination environments of Ln3+ ions bonded with the mixed anions, which provides a wide variety of means to modulate the NIR luminescence of Ln3+ complexes.A series of hetero-trinuclear Zn2Ln complexes [Zn2Ln(L)2(NO3)2(SCN)(Py)2] (Ln = Nd, 1; Ln = Yb, 2; Ln = Er, 3 and Ln = Gd, 4) are obtained from the further reaction of Ln(NO3)3·6H2O and KSCN on the condition of stoichiometry control with the Zn-Schiff-base [ZnL(Py)] precursor from the pure Salen-type Schiff-base ligand H2L (H2L = N,N′-bis(salicylidene)ethylene-1,2-diamine), respectively. The correlation between the molecular structures and the photophysical properties shows their NIR luminescent properties are hypersensitive to the composition and symmetry of the coordination environments of Ln3+ ions bonded with the mixed anions, which provides a wide variety of means to modulate the NIR luminescence of Ln3+ complexes.Display Omitted► Through the adjustment of the chemical environment of 4f ions induced by mixed anions in the series of trinuclear Zn2Ln complexes of the pure Salen-type Schiff-base ligands, the modulation of their NIR luminescence should be relatively effective. ► hetero-trinuclear Zn2Ln complexes; ► effective modulation of NIR luminescence; ► mixed anions inducement.
Keywords: Adjustment of coordination environment; Zn2Ln arrayed Schiff-base complexes; Sensitization and energy transfer; Modulation of NIR luminescence;

Correlation between the SOD-like activity of hexacoordinate iron(II) complexes and their Fe3+/Fe2+ redox potentials by Balázs Kripli; Gábor Baráth; É. Balogh-Hergovich; Michel Giorgi; A. Jalila Simaan; László Párkányi; József S. Pap; József Kaizer; Gábor Speier (205-209).
Hexacoordinate, high-spin iron(II) complexes with different isoindoline-derivative ligands have been prepared and characterized. The Fe3+/Fe2+ redox transition is reversible in each case, but the E 1/2 values vary in a ~ 400 mV range depending on the ligand. SOD-like activity of the complexes was determined by indirect methods with cytochrome c, and nitroblue tetrazolium indicator at pH 7.6. The measured activities correlate with the redox potentials for the Fe3+/Fe2+ couples. The results indicate that the superoxide dismutation takes place via an inner-sphere mechanism at the iron site.Hexacoordinate, high-spin iron(II) complexes with different isoindoline-derivative ligands have been prepared and characterized. The Fe3+/Fe2+ redox transition varies in a ~ 400 mV range depending on the ligand. SOD-like activity of the complexes correlates with the redox potentials for the Fe3+/Fe2+ couples. The results indicate that the superoxide dismutation takes place via an inner-sphere mechanism at the iron site.Display Omitted► High-spin Fe(II) complexes with isoindoline-based ligands synthesized and characterized. ► The Fe3+/Fe2+ redox transitions span a ~400 mV range. ► SOD-like activity of the complexes correlates with the redox potentials.
Keywords: Iron; SOD mimics; Isoindoline ligand; Redox chemistry;

An unusual type of oxidative addition of disulfides containing a carboxylic acid group to platinum(II) is established, giving the first thiolate–carboxylate complexes of platinum(IV). The disulfide R2S2 with R = CH2CH2CO2H reacts with [PtMe2(2,2′-bipyridine)] to give RSH and the chelating thiolate–carboxylate complex [PtMe22-S,O–SCH2CH2CO2)(bipy)]. However, the disulfide R2S2 with R = C6H3–4–NO2–3–CO2H reacts to give first the product of trans oxidative addition [PtMe2(SR)2(bipy)], which slowly reacts further to give RSH and the bridging thiolate–carboxylate complex [Pt2Me42S,O–SC6H3–4–NO2–3–CO2)2(bipy)2].The first chelating and bridging thiolate–carboxylate complexes of platinum(IV) are prepared by an unusual oxidative addition reaction.Display Omitted►oxidative addition of disulfides containing a carboxylic acid group to platinum(II) ►first synthesis of chelating and bridging thiolate–carboxylate complexes of platinum(IV) ►structure of bridging thiolate–carboxylate complex [Pt2Me42S,O–SC6H3–4–NO2–3–CO2)2(bipy)2]
Keywords: Platinum; Oxidative Addition; Disulfide; Thiolate; Carboxylate;

The first heterometallic Mn–Ca cluster containing exclusively Mn(III) centers by Vasiliki Kotzabasaki; Milosz Siczek; Tadeusz Lis; Constantinos J. Milios (213-216).
The reaction of Mn(ClO4)2·6H2O with Ca(prop)2 and Me-saOH2 in MeCN yields the heterometallic polymeric complex {[MnIII 6Ca2O2(Me-saO)6(prop)6 (H2O)2].2MeCN.0.95H2O}n (1) (prop = propionate; Me-saOH2  = 2-hydroxyphenylethanone oxime). Complex 1 consists of hexanuclear centrosymmetric [MnIII 6O2(Me-saO)6]2+ units bridged by propionate calcium [Ca2(prop)6]2− centrosymmetric dimers. Magnetic measurements show that the hexanuclear magnetic core has an S  = 4 ground state.The synthesis and magnetic properties of a mixed-metal [MnIII 6 CaII 2] polymeric complex are reported.Display Omitted►Photosystem II. ►Manganese–calcium cluster. ►Magnetism/
Keywords: Oximate manganese calcium complexes; Heterometallic complexes; Photosystem II; Magnetic properties;

Three new coordination polymers, namely [Mn2(5-phenoxonicotinato)2] ( 1 ), [Cd2(5-phenoxonicotinato)2] ( 2 ), and [Fe2(5-phenoxonicotinato)2] ( 3 ), have been synthesized under hydrothermal conditions and characterized structurally by single-crystal X-ray diffraction. The structure of compound 1 can be described as a 3D metal-organic framework which is constructed by two kinds of crystallographical unique Mn cations and one kind of μ 6-5-phenoxonicotinato bridging ligand, featuring a 6,6-connected {3·410·64}{49·66} topology structure. Taking Cd and Fe ions in place of Mn ions respectively, two new compounds 2 and 3 are successfully obtained which are isostructural with 1. In addition, the magnetic property of compound 1 is investigated in detail.Three new 3D coordination polymers, [M(II)2(5-phenoxonicotinato)2]n, (M = Mn 1, M = Cd 2, and M = Fe 3) constructed by two kinds of structurally independent metal ions with one kind of μ 6-5-phenoxonicotinato bridge are isostructural and exhibit a novel 6,6-connected {3·410·64}{49·66} topology structure. The study on magnetic property of compound 1 reveals that antiferromagnetic interactions exist between the neighboring Mn(II) ions.Display Omitted► 5-hydroxynicotinic acid can coordinate with Mn(II)/Cd(II)/Fe(II) ions directly forming 3D MOFs. ► The three 3D MOFs exhibit a novel 6,6-connected {3·410·64} {49·66} topology structure. ► The stratagem for synthesizing the three 3D MOFs simplifies crystal engineering. ► Compound 1 reveals antiferromagnetic interactions between the neighboring Mn(II) ions.
Keywords: Coordination polymers; 5-hydroxynicotinic acid; Magnetic property; Crystal structures;

Synthesis and characterization of Zn2+/Cd2+ doped polyoxometalate microtubes by Yan Shen; Jun Peng; Changyun Chen; Huanqiu Zhang; Cuili Meng; Xinglin Li (221-224).
Metal ions doped polyoxometalate (POM) microtubes (M–SiW12; M = Zn2+, Cd2+) have been synthesized in aqueous solution by a simple method. The microtubes were characterized by FT-IR, UV/Vis, XPS, elemental analysis, and their morphology was examined by ESEM-FEG. The Zn2+ or Cd2+ doped in POM microtubes were chelated with 8-hydroxyquinoline, to obtain novel POM microtubes (MQ2–SiW12) with fluorescence.The Zn2+ and Cd2+ doped 12-tungstosilicate microtubes (Zn–SiW12 and Cd–SiW12) have been obtained from aqueous solution by a simple method, and the obtained microtubes exhibited intense fluorescence after further modifying by 8-hydroxyquinoline.Display Omitted►The Zn2+ and Cd2+ ions doped POM microtubes were synthesized. ► The doped Zn2+ and Cd2+ ions were chelated with 8-hydroxyquinoline. ► The obtained MQ2–SiW12 microtubes maintained the microtubular morphology. ► The obtained MQ2–SiW12 microtubes exhibited intense fluorescence.
Keywords: Polyoxometalates; Doped; Microtubes; 8-hydroxyquinoline metal chelates; Photoluminescence properties;

Synthesis, structural and emission studies of a bis (carbamoyl methyl) sulfone complex of uranyl nitrate by Shanmugaperumal Kannan; Sadhan B. Deb; Micheal G.B. Drew (225-227).
A new tri-functional ligand iBu2NCOCH2SO2CH2CONiBu2 (L) was prepared and characterized. The coordination chemistry of this ligand with uranyl nitrate was studied with IR, 1HNMR, ES-MS, TG and elemental analysis methods. The structure of the compound [UO2(NO3)2L] was determined by single crystal X-ray diffraction techniques. In the structure the uranium(VI) ion is surrounded by eight oxygen atoms in a hexagonal bi-pyramidal geometry. Four oxygen atoms from two nitrate groups and two oxygen atoms from the ligand form a planar hexagon. The ligand acts as a bidentate chelate and bonds through both the carbamoyl groups to the uranyl nitrate. An ES-MS spectrum shows that the complex retains the bonding in solution. The compound displayed vibronically coupled fluorescence emission.The coordination chemistry of a new tri-functional ligand iBu2NCOCH2SO2CH2CONiBu2 with uranyl nitrate shows that it acts as a bidentate chelating ligand and bonds through both the carbamoyl groups to the uranyl nitrate. The uranium(VI) ion is surrounded by eight oxygen atoms in a hexagonal bi-pyramidal geometry.Display Omitted► Synthesis of bis(carbamoyl methyl) sulfone ligand. ► Complex chemistry of bis(carbamoyl methyl) sulfone with uranyl nitrate. ► Structure of [UO2(NO3)2(iC4H9)2NCOCH2)2SO2] compound. ► ES-MS and Emission spectrum of [UO2(NO3)2(iC4H9)2NCOCH2)2SO2].
Keywords: Bis(carbamoyl methyl ) sulfone; Uranium(VI); Crystal structure; Emission spectrum; ES-MS spectrum;

Presented here is a new photoluminescent homochiral Cd(II) camphorate with auxiliary 2-(4-pyridyl)benzimidazole ligand, which is the first homochiral metal-organic framework adopting the 5-connected BN topology.A new photoluminescent homochiral Cd(II) camphorate with auxiliary (4-pyridyl)benzimidazole ligand is hydrothermally synthesized and structurally characterized, which is the first homochiral metal-organic framework adopting the 5-connected BN topology.Display Omitted► A new homochiral Cd(II) camphorate with 4-PyBIm as the auxiliary ligand. ► Rare 5-connected BN topology in homochiral framework. ► Interesting homochiral framework with photoluminescent property.
Keywords: Crystal structure; Cadmium; Hydrogen bond; Topology; Homochiral;

Unusual (4,6)-connected lanthanide 1,3-phenylenediacetate coordination frameworks displaying lanthanide contraction effect and 1D and 2D mixed self-weaving architecture by Yi-Xia Ren; Mei-Li Zhang; Dong-Sheng Li; Feng Fu; Ji-Jiang Wang; Miao Du; Xiang-Yang Hou; Ya-Pan Wu (231-234).
A series of 2D Ln-organic coordination frameworks (Ln = Sm3+ for 1, Eu3+ for 2, Tb3+ for 3, and Ho3+ for 4) with (4,6)-connected (44.52)(44.5.6)(44.54.66.7) topology has been constructed, in which 1D zigzag chains and 2D (4,4) networks intertwine mutually into the unusual 1D and 2D mixed self-weaving patterns. Interestingly, due to the lanthanide contraction effect, the 9-coordinated geometries of the Ln(III) ions gradually transform from triangle tetrakaidecahedron (Sm3+ and Eu3+), to a three-capped triangle prism (Eu3+ and Tb3+), and then to a single-capped anti-square prism (Ho3+).Four Ln-organic coordination frameworks (Ln = Sm3+, Eu3+, Tb3+, and Ho3+) with (4,6)-connected (44.52)(44.5.6)(44.54.66.7) topology are described, in which 1D zigzag chains and 2D (4,4) networks intertwine mutually into an unusual 1D and 2D mixed self-weaving motif. Lanthanide contraction effect is also observed to regulate the coordinated geometries of Ln(III) and the overall 3D lattices.Display Omitted► In this manuscript, we report a series of 2D Ln-organic coordination frameworks (Ln = Sm3+ for 1, Eu3+ for 2, Tb3+ for 3, and Ho3+ for 4) with (4,6)-connected (44.52)(44.5.6)(44.54.66.7) topology, in which 1D zigzag chains and 2D (4,4) networks intertwine mutually into the unusual 1D&2D mixed self-weaving patterns. ► Interestingly, due to the lanthanide contraction effect, the 9-coordinated geometries of the Ln(III) ions gradually transform from triangle tetrakaidecahedron (Sm3+ and Eu3+), to three-capped triangle prism (Eu3+ and Tb3+), and then to single-capped anti-square prism (Ho3+). ► In this point, the 1,3-pda ligand shows an excellent potential in the formation of new Ln3+ coordination frameworks. Also, the 1D&2D mixed self-weaving architectures observed herein provide new perspectives in Ln-carboxylate coordination chemistry. Additionally, thermal stability and fluorescence of these new materials have also been studied. ► These results will enrich the current research of the flexible ligand on constructing Ln-coordination polymers and provide new insights into its application in designing such crystalline materials with desired structures and properties.
Keywords: Lanthanide(III) complexes; Crystal structures; Luminescent properties;

Reaction of 9-trimethylsilylfluorenyllithium with nitriles: Organolithium compounds by Xia Chen; Xiaoyan Xue; Liping Zhang; Wen-Hua Sun (235-237).
The reaction of 9-trimethylsilylfluorenyllithium (C13H8SiMe3)Li ( 1 ) with α-hydrogen-free nitriles gave highly sensitive lithium compounds, (η3-C13H8SiMe3)Li( t BuCN)(Et2O) ( 2 ), [η3-(C13H8)C(NMe2)N(SiMe3)]Li (Et2O)2 ( 3 ) and [η36-(C13H8)C(Ph)N(SiMe3)Li]2 ( 4 ), illustrating bonding features of η3-allyl, η3-azaallyl, and η6-arene interactions.The reaction of 9-trimethylsilylfluorenyl lithium with α-hydrogen-free nitriles was carried out to obtain the highly sensitive lithium compounds, which showed a bonding library of lithium with ligands acting as η3-fluorenyl, η3-azaallyl, and η6-arene interactions, and donating bonding.Display Omitted► The 9-trimethylsilylfluorenyllithium (C13H8SiMe3)Li reacted with three α-hydrogen-free nitriles. ► The lithium intermediates were isolated and characterized. ► The different bonding features of η3-allyl, η3-azaallyl, and η6-arene interactions were observed between lithium and ligands.
Keywords: 9-trimethylsilylfluorenyllithium; η3-allyl; η3-azaallyl; η6-arene;

Rhenium(I) and technetium(I) complexes of a novel pyridyltriazole-based ligand containing an arylpiperazine pharmacophore: Synthesis, crystal structures, computational studies and radiochemistry by Achour Seridi; Mariusz Wolff; Alexandre Boulay; Nathalie Saffon; Yvon Coulais; Claude Picard; Barbara Machura; Eric Benoist (238-242).
The preparation of two M(CO)3 complexes (M = Re and 99mTc) from a novel pyridyltriazole-based ligand 2 bearing the bioactive (2-methoxyphenyl)piperazine pharmacophore are described. Spectral data, X-ray structure and DFT calculations of the rhenium(I) complex as well as the 99mTc-labelling of 2 are reported. Both complexes were neutral and iso-structural. Moreover, the 99mTc-complex presented a suitable lipophilic character for its use as a CNS imaging agent.The preparation of two M(CO)3 complexes (M = Re and 99mTc) from a novel pyridyltriazole-based ligand 2 bearing the bioactive (2-methoxyphenyl)piperazine pharmacophore are described. Spectral data, X-ray structure and DFT calculations of the rhenium(I) complex as well as the 99mTc-labelling of 2 are reported. Both complexes were neutral and iso-structural. Moreover, the 99mTc-complex presented a suitable lipophilic character for its use as a CNS imaging agent.Display Omitted► A novel pyridyltriazole-based ligand bearing a bioactive moiety is reported. ► the corresponding Re- and Tc-complexes were neutral and iso-structural. ► 99mTc-complex presented a suitable lipophilicity for its use as a CNS imaging agent.
Keywords: Click chemistry; Bidentate ligands; Rhenium; Technetium; X-ray structure; DFT calculations;

Two new mercury(II) complexes [Hg(TDMPT)Cl2] (1) and [Hg37(TDMPT)12Br74] (2) (TDMPT = 2,4,6-tris(3,5-dimethylpyrazolyl)-1,3,5-triazine) have been prepared and characterized by X-ray structural analysis. Mercury(II) complex 1 is a mononuclear coordination compound. Meanwhile, mercury(II) complex 2 is the first example of the 3D coordination polymer with a 1D inorganic chain based on the Lindqvist-type [Hg6Br19]7− anion as building blocks. Furthermore, the bromide anions act as terminal, μ2- and μ6-bridge ligands.The first example of the 3D coordination polymer with a 1D inorganic chain based on the Lindqvist-type [Hg6Br19]7− anion as a building block has been reported.Display Omitted► The Lindqvist-type [Hg6Br19]7- anion as building blocks. ► A three dimensional metal-organic framework with one dimensional inorganic chain. ► The TDMPT ligand adopts a novel coordination mode, namely, a tetradentate with a terpyridine-like tridentate and a monodentate.
Keywords: Lindqvist-type anion; 1D Inorganic chain; Mercury ion cluster; Bromide ion cluster; 3D framework;

One new 2D cadmium-organic framework containing 2,4′-biphenyldicarboxylate ligand by Xiao-Yi Yi; Pei-Yi Yin; Long Tong; Zhi-Gang Gu; Jin-Hao Chen; Hong-Guang Jin; Shan-Shan Li; Xue Gong; Yue-Peng Cai (247-250).
One new 2D framework constructed from one-dimensional nano-channels hinged by two meso-helical chains sharing two different Cd centers through 2,4′-bpdc2− ligands, which denotes the first example of the complex including single 2,4′-biphenyldicarboxylic acid ligand.Display Omitted► One new 2D framework constructed from one-dimensional nano-channels hinged by two meso-helical chains sharing two different Cd centers through 2,4′-bpdc2- ligands, which denotes the first example of the complex including single 2,4′- biphenyldicarboxylic acid ligand.
Keywords: 2D cadmium-organic framework; 2,4′-biphenyldicarboxylate; meso-helix; Fluorescence;

Electronic and molecular structure of [Cr(N)(NCO)4]2−, the first example of a mixed nitride–cyanate complex by Theis Brock-Nannestad; Anders Hammershøi; Magnus Schau-Magnussen; Johan Vibenholt; Jesper Bendix (251-253).
Metathesis of [Cr(N)Cl4]2− with excess cyanate affords the title complex which is the first example of a nitride complex with only cyanate auxiliary ligands. The electronic spectrum allows assignment of the ligand field transitions: B1(C4v) ← B2(C4v) and E(C4v) ← B2(C4v). From these data, cyanate can be deduced to be intermediate between azide and thiocyanate with respect to σ-donation and comparable to thiocyanate, but weaker than azide with respect to π-donation. Solution EPR demonstrates the cyanate ligands to be N-bonded with similar super-hyperfine couplings to all nitrogen ligators, and the X-ray crystal structure of (Ph3PNPPh3)2[Cr(N)(NCO)4] ( 1 ) establishes the expected 5-coordinate square pyramidal structure with a short Cr–N(nitride) bond, 1.520(5) Å and chromium–cyanate bond lengths in the range 1.948(12)–2.05(2) Å.As the first example of a complex with only nitride and cyanate ligands, [Cr(N)(NCO)4]2− was prepared by metathesis from the chloro complex. The cyanate ligands are N-bonded and intermediate between azide and thiocyanate in ligand field strength.Display Omitted► Metathesis reactions of Cr(V) nitride complexes. ► Structural comparison of pseudo halide complexes. ► d–d transitions in UV–vis spectroscopy. ► Cyanate ligand-field strength. ► Fitting of EPR spectral traces.
Keywords: Nitride; Cyanate; EPR; Electronic structure; Ligand-field; Metathesis;

Controlling the ratio of 2,2′-bpy to benzene-1,3,5-tricarboxylic acid produces an interesting complex, namely [Co2(2,2′-bpy)6]·(btca)·Cl·11H2O (H3btca = benzene-1,3,5-tricarboxylic acid, 2,2′-bpy = 2,2′-bipyridine). We report the structural evidence in the solid state of discrete (H2O)11 conformation. This unit is found to act as supramolecular glue in the aggregation of cobalt (II) complex to give a three-dimensional cage-like network through hydrogen-bonding. It is interesting that the structure contains 3D negatively charged cage. The preliminary investigation on the fluorescence property of the complex is presented.A novel Co (II) complex with 2,2′-bpy ligand, which contains supramolecular (H2O)11 morphology. The hydrogen-bonding association leads to the formation of the infinite morphology of water molecules.Display Omitted► Cobalt complex [Co2(2,2'-bpy)6]4+ pillars 2D layers of organic anions [(BTCA).11(H2O)]3-. ► The structure contains 3D negatively charged cage. ► Dual host-guest structure features including water clusters.
Keywords: Complexes; Water undici; Negatively charge; Fluorescence property;

A new lanthanum sulfate Na[C6H14N2][La3(SO4)6(H2O)3] 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR and TGA. Structure analysis indicates that the structure of 1 features unusual three-dimensional inorganic framework constructed from La–O–S tubes and cubic cages. The Na+ plays an important role in the formation of 3-D open framework of 1.The structure of 1 features a novel three-dimensional inorganic framework constructed from La–O–S tubes and cubic cages. The Na+ plays an important role in the formation of new 3-D open framework of 1.Display Omitted► A Na+ templated new 3-D lanthanum sulfate Na[C6H14N2][La3(SO4)6(H2O)3] 1 has been synthesized. ► The open framework of 1 is constructed from La-O-S tubes and cubic cages. ► The tubes and cubic cages formed a 3-D structure in a cross arrangement.
Keywords: Hydrothermal synthesis; Lanthanum sulfates; Crystal structures; 3D framework; Template;

A new three-dimensional coordination polymer, based on mixed-bridged biphenyl-2,2′,6,6′-tetracarboxylate/1,2,4-triazole, has been hydrothermally synthesized and structurally characterized. The magnetic property study indicates the compound shows a weak antiferromagnetic behavior, which mainly arises from the antiferromagnetic coupling interaction in the one-dimensional [Co(COO)] n chains through synanti carboxylate bridges.Display Omitted► A new three-dimensional coordination polymer has been hydrothermally synthesized and structurally characterized. ► The polymer is built by two-dimensional layers and neutral pillars. ► The magnetic property study indicates that the compound shows a weak antiferromagnetic behavior.
Keywords: Biphenyl-2,2′,6,6′-tetracarboxylate; 1,2,4-Triazole; Co(II) complex; Antiferromagnetic;

Tris(benzenethiolato)indium(III) (In(SPh)3) has been facilely prepared in high yield of 95.0% by a microwave-assisted solvothermal reaction of indium and diphenyl disulphide in methanol in 15 min. The combination of In(SPh)3 as precursor with dipyridyl ligands of bipy (bipy = 4,4′-bipyridine) and dpp (dpp = 1,3-di(4-pyridyl)propane) in methanol at ambient conditions yielded two new compounds, namely In(SPh)3(bipy) (1) and In(SPh)3(dpp) (2), respectively. Single-crystal X-ray crystallographic studies reveal that in both the structures, the five-coordinated In(III) ions in nearly perfect trigonal–bipyramidal geometry are interconnected by the bifunctional dipyridyl ligands to form one-dimensional chains. Their thermal properties have been investigated.In(SPh)3 has been facilely prepared by a microwave-assisted reaction of indium and diphenyl disulphide in methanol. The combination of In(SPh)3 as precursor with dipyridyl ligands of bipy (bipy = 4,4′-bipyridine) and dpp (dpp = 1,3-Di(4-pyridyl)propane) at ambient conditions yielded two new compounds, namely In(SPh)3(bipy) (1) and In(SPh)3(dpp) (2), respectively.Display Omitted► In(SPh)3 is prepared by a microwave-assisted reaction. ► In(SPh)3 is used as precursor to combine with dipyridyl ligands to yield two new compounds, namely In(SPh)3(bipy) (1) and In(SPh)3(dpp) (2). ► The crystal structures of In(SPh)3(bipy) (1) and In(SPh)3(dpp) (2) feature one-dimensional chains.
Keywords: Microwave-assisted; Synthesis; Metal thiolate; Precursor; Crystal structure;

A linear Cu (II) coordination polymer based on a simple click chelator by Yang Fu; Hua Li; Xingguo Chen; Jingui Qin (268-270).
A linear Cu(II) coordination polymer [CuCl2Cu(N3)2L] (L  = 2-[(4-phenyl-5 H-1,2,3-triazole)methyl]pyridine) (1) has been synthesized. The crystal structure is determined by the single crystal X-ray diffraction. It is found that Cu(II) cations in 1 are bridged with four types of ligand or anions, 1,2,3-triazole group in L, two different End-Open azides and a tri-coordinated chloride anion. Among them L simultaneously behaves as a chelator and a bridge, in which the N2 and N3 atoms of 1, 2, 3-triazole group coordinate to different Cu(II) cations. The Cu(II) centers exhibit two different coordination geometries in 1. One Cu(II) cation adopts a distorted octahedral geometry and the other adopts a distorted square pyramidal geometry. The magnetic measurement indicates that 1 exhibits the paramagnetism with anti-ferromagnetic interaction among the Cu(II) spins.A linear coordination polymer, Cu(Cl)2Cu(N3)2 L (L  = 2-[(4-phenyl-5H-1,2,3-triazole) methyl]pyridine) (1), has been synthesized. In 1, L behaves simultaneously as a chelator and a bridge, and another two types of bridging ligands, end-open azide and chloride anion, also participate in coordination. 1 exhibits paramagnetism with anti-ferromagnetic interaction among the Cu(II) spins.Display Omitted► Simple click chelator L (L  = 2-[(4-Phenyl-5 H-1, 2, 3-triazole) methyl] pyridine) compose linear coordination polymer [CuCl2Cu(N3)2L]. ► L behaves simultaneously as both a chelator and a bridging ligand through the 1, 2, 3-triazole group. ► Both N2 and N3 in L coordinated to different copper (II). ► The N2 is more effective than N3 in the polymeric structure. ►Two EO bridged azido anions and a tri-coordinated chloride anion also involved in complex.
Keywords: Cu(II) complexes; Coordination polymer; Click chelator; Crystal structure; Magnetic property;

Aluminum complexes bearing ligand O,O-bidentate dipyrazolate are synthesized and structurally characterized. The reaction of 4-methylidene-bis(1-phenyl-3-methylpyrazol-5-one) (MBP-H) with AlMe3 (1.2 molar equiv) in toluene yields [(MBP)AlMe2] (1) as the four-coordinate monomeric aluminum complex. Tri-adduct complex [Al(MBP)3] (2) results from treatment of AlMe3 with MBP-H (3 molar equiv) in toluene in a high yield. In the presence of 9-anthracenemethanol, mono-adduct aluminum complex 1 catalyzes efficiently the ring-opening polymerization of ε-caprolactone (ε-CL) in a controlled manner, yielding PCLs with the expected molecular weights and narrow polydispersity indices (PDIs).Reactions of 4-methylidene-bis(1-phenyl-3-methylpyrazol-5-one) with trimethylaluminum: synthesis, structure and catalysis for the ring-opening polymerization of ε-caprolactone.Display Omitted► Aluminum complexes bearing the MBP ligand are synthesized and fully characterized. ► Complex 1 catalyzes the polymerization of ε-caprolactone in a “controlled” fashion. ► Al complex 1 catalyzes the polymerization of ε-caprolactone in an “immortal” manner.
Keywords: Aluminum complex; Catalyst; O,O-bidentate; Ring-opening polymerization; ε-caprolactone;

Reactions of bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) with (pyH)5[MoOCl4(H2O)]3Cl2, and (pyH)[MoOBr4] in acetonitrile at elevated temperatures result in obtaining two new compounds, [MoOX2(bdmpza)]∙yCH3CN (X=Cl y = 0 (1), X=Br, y = 1 (2)), respectively. The treatment of mononuclear 1 and 2 in acetonitrile/water solution gives dinuclear [Mo2O4(bdmpza)2]∙2H2O (3). The complexes were analyzed by elemental analysis UV–Vis and IR spectroscopy. The κ 3-N,N,O coordination of Mo atoms by bdmpza was proven by the single-crystal X-ray structure. In all compounds the Mo(V) centers are six-coordinated; in 3 the Mo atoms in cis-{Mo2O4}2+ core are bridged by two O atoms.Two novel oxo-bridged mononuclear neutral Mo(V) complexes have been prepared by reaction of [MoVO(H2O)Cl4] with tripodal heteroscorpionate N,N,O-ligand (Hbdmpza), [MoOX2(bdmpza)] (X=Cl, 1; Br, 2). By reaction of 1 or 2 with H2O in an acetonitrile/water mixture of 1:1 ratio a dinuclear complex [Mo2O4(bdmpza)2]∙2H2O (3) is obtained. In all compounds the Mo(V) centers are six-coordinated; in 3 the Mo atoms in cis-{Mo2O4}2+ core are bridged by two O atoms and connected by a Mo–Mo bond.Display Omitted► Synthesis of Mo(V) complexes with N,N,O-scorpionate ligand Hbdmpza. ► Complexes: [MoOCl2(bdmpza)] [MoOBr2(bdmpza)]∙CH3CN, and [Mo2O4(bdmpza)2]∙2H2O. ► X-ray crystal structure analysis, IR and UV–Vis spectra of complexes.
Keywords: Scorpionate ligands; Hbdmpza; Molybdenum(V); X-ray structure;

One novel organic–inorganic hybrid compound, (EB-NH3 +)(18-crown-6)·H2PO4 ·2H3PO4·2.5H2O (1) (EB-NH3 + = 4-ethoxybenzenammonium; 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclo-octadecane), has been synthesized and characterized by powder X-ray, IR, thermogravimetric analysis and single X-ray structure analysis. In the structure of complex 1 the organic (EB-NH3 +)(18-crown-6) supermolecular cation sheet and inorganic phosphate anion sheet arrange alternately. Compound 1 and its deuterium product 2 display excellent dielectric property with a huge dielectric permittivity deuterated effect (DEF) of 1649% (200 Hz, 300 K).In the novel organic-inorganic hybrid compound 1, organic supermolecular cation and inorganic phosphate anion sheet arrange alternately. The frequency-dependent and temperature-dependent dielectric constants measurement shows that compound 1 and its deuterium product 2 display excellent dielectric property with a huge dielectric permittivity deuterated effect (DEF) of 1649% (200Hz, 300K).Display Omitted► We report one organic-inorganic hybrid compound in which the organic (EB-NH3 +)(18-crown-6) supermolecular cation sheet and inorganic phosphate anion sheet arrange alternately. ► This compound and its deuterium product display a huge dielectric permittivity deuterated effect. ► The huge dielectric DEF is due to the great dielectric response of water molecules.
Keywords: 4-Ethoxybenzenammonium; Dihydric phosphate; Crown ether; Dielectric permittivity; Deuterated effect;

Two ternary coordination polymers with the same ingredients but different structures, [Zn2(datrz)2(nip)]n (1) and {[Zn(Hdatrz)(nip)]·H2O}n (2) (Hdatrz = 3,5-diamino-1,2,4-triazole; nip2−  = 5-nitroisophthalate), were respectively obtained by temperature-controlled hydrothermal reactions and fully structural characterized. Interestingly, tetrahedral ZnII ions in 1 are linked into wavy layers by anionic μ 3-N1,N2,N4-datrz ligands, which are further supported by deprotonated bis-monodentate nip2− to generate a 3D pillared-layer framework. In contrast, the tetrahedral ZnII ions in 2 are aggregated into a (4, 4) covalent layer through alternate μ 2-N1,N4-Hdatrz and bis-monodentate nip2− bridges. Thus, the competitive binding of the two polydentate ligands to the metal ion plays essential roles on the connectivity and dimensionality of the two complexes. Thermal stability and the fluorescent emissions of the two complexes were also investigated and compared.Two fluorescent polymers with the same components but different structures, 3D pillared-layer framework for 1 and 2D (4, 4) grid-layer for 2, were hydrothermally obtained by varying the reaction temperature. Their structural diversity is significantly resulted from the competitive coordination of the mixed ligands towards tetrahedral ZnII ion.Display Omitted► Two polymers with the same components but different structures, 3D pillared-layer framework for 1 and 2D (4, 4) grid-layer for 2, were hydrothermally obtained by varying the reaction temperature. ► The structural diversity of the two complexes is significantly resulted from the competitive coordination of the mixed ligands towards tetrahedral ZnII ion.
Keywords: Assembly; Pillared-layer framework; 3,5-Diamino-1,2,4-triazole; 5-Nitroisophthalate;

Crystalline Cu–PbO ceramic composite thin films from Pb2(OAc)4(μ-O)3Cu6(dmae)4Cl4·(C7H8)·1.7(H2O) by Muhammad Shahid; Mazhar Hamid; Muhammad Mazhar; Javeed Akhtar; Matthias Zeller; Allen D. Hunter (288-291).
Pb–Cu heterobimetallic precursor complex 1, Pb2(OAc)4(μ-O)3Cu6(dmae)4Cl4 ·(C7H8)·1.7(H2O) [dmae =  N,N-dimethylaminoethanolate ((CH3)2NCH2CH2O¯), OAc = acetate (CH3COO¯)] was synthesized through a simple chemical route and crystallized in the monoclinic space group C2/c. The precursor was characterized by its melting point, elemental composition, FT-IR, MS and by X-ray single crystal structure determination. Thin films were deposited by aerosol assisted chemical vapor deposition on a glass substrate and characterized for adhesion, SEM/EDX and XRD. These studies reveal it to be a suitable precursor for the deposition of Cu–PbO ceramic composite thin films at a relatively low temperature of 450 °C.Pb–Cu heterobimetallic complex Pb2(OAc)4(μ-O)3Cu6(dmae)4Cl4 ·(C7H8)·1.7(H2O) (1) synthesized by simple chemical technique, is decomposed directly under AACVD conditions to give Cu–PbO composite thin films which were characterized by XRPD and SEM/EDX.Display Omitted► Pb–Cu heterobimetallic complex Pb2(OAc)4(μ-O)3Cu6(dmae)4Cl4 ·(C7H8)·1.7(H2O) is synthesized by simple chemical technique. ► The complex decomposes directly under AACVD conditions at a relatively low temperature of 450 °C to give Cu–PbO composite thin films. ► TGA, XRD and SEM/EDX results reveal it to be a suitable precursor for the deposition of phase pure Cu–PbO ceramic composite thin films.
Keywords: Bimetallic complex; CVD precursor; PXRD; Copper–lead oxide composite; SEM/EDX;

The reaction of [PtCl2(cod)] (cod = 1,5-cyclooctadiene) with Ph-Ph′-Ph′(2,3-NH2)-Ph′-Ph (LH 2 ) (Ph = phenyl; Ph′ =  p-phenylene; Ph′(2,3-NH2) =  p-phenylene-2,3-diamine) gave a new platinum(II) complex bearing a π-conjugated Ph-Ph′-Ph′(2,3-NH)-Ph′-Ph (L, Ph′(2,3-NH) = p-phenylene-2,3-diamide) ligand, [Pt(L)(cod)], with the liberation of 2 HCl. The X-ray structure determination of the complex confirmed the coordination of the ligand to the platinum center in an o-benzenediamide form. The cyclic voltammogram of the complex showed reversible two-step [Pt-bda]0/[Pt-sqdi]+ and [Pt-sqdi]+/[Pt-bqdi]2+ redox couples (bda =  o-benzenediamide, sqdi =  o-semiquinone diimine, bqdi = o-benzoquinone diimine).A new Pt complex bearing the Ph-Ph′-Ph′ (2,3-NH)-Ph′-Ph (L) ligand [Pt(L)(cod)] was prepared, and its crystal structure and electrochemical properties were elucidated. The cyclic voltammogram of the complex showed reversible two-step redox couples based on the ligand L.Display Omitted► A new Pt complex bearing a Ph-Ph′-Ph′(2,3-NH)-Ph′-Ph ligand was prepared. ► The ligand is coordinated to the platinum center in an o-benzenediamide form. ► The CV of the complex showed reversible two-step redox couples based on the ligand.
Keywords: Platinum complex; Benzenediamide; X-ray structure; Electrochemistry; DFT calculation;

Electropolymerization and characterization of an alternatively conjugated donor–acceptor metallopolymer: Poly-[Ru(4′-(4-(Diphenylamino)phenyl)-2,2′:6′,2″-Terpyridine)2]2+ by Dongfang Qiu; Qian Zhao; Xiaoyu Bao; Kecheng Liu; Hongwei Wang; Yingchen Guo; Lianfeng Zhang; Junliang Zeng; Huan Wang (296-299).
A functionalized complex [Ru(L)2](PF6)2 {L  = 4′-[4-(diphenylamino)phenyl)]-2,2′:6′,2″-terpyridine} was synthesized and characterized by 1 H NMR, 13 C NMR and elemental analyses. Its oxidative electropolymerization was 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 red hybrid polymer film, characterized by X-ray photoelectron spectroscopy (XPS), exhibited a non-diffusional charge transfer behaviour for Ru(III)/Ru(II) couple and an irreversible redox process of triphenylamine moiety on the Pt working electrode, as well as high stability in monomer-free electrolytic solution. The film thickness was easily tuned by controlling the number of potential sweeping cycle, and the AC impedance of as-formed film increased with cycling number. Morphological characterization of the film on indium tin oxide (ITO) was provided by scan electron microscopy (SEM) and atomic force microscopy (AFM). The donor–acceptor (D–A) polymer film on ITO showed a broad and red-shifted 1 MLCT wave in the UV–vis spectrum and a clearly electrochromic behaviour from red to black in the spectroelectrochemical study.A D–A metallopolymer film: The Ru(II)-terpyridine complex with triphenylamine functional groups has been electrochemically deposited on Pt or ITO electrode to form a red polymer film containing in-chain metal centers, which shows unique electrical and optical activities.Display Omitted► Electron-donating triphenylamine groups as electro-active moieties. ► Electron-deficient [Ru(terpyridine)2]2+ core stabilizes the radical cation species. ► D-A metallopolymer film with tunable thickness and granularly 3D morphology. ► Non-diffusional redox process in the well-adhered polymer film. ► A broad and red-shifted 1MLCT wave and a clearly electrochromic behaviour.
Keywords: Electropolymerization; Ru(II)-terpyridine complex; Triphenylamine; Donor–acceptor polymer;

Two coordinated-solvent directed zinc(II) coordination polymers with rare gra topological 3D framework and 1D zigzag chain by Mei-Ling Cheng; Enjing Zhu; Qi Liu; Sheng-Chun Chen; Qun Chen; Ming-Yang He (300-303).
Two novel coordination polymers [Zn2(tfbdc)2(DMF)2(EtOH)]n (1) and [Zn(tfbdc)(MeOH)4]n (2) have been prepared by reactions of Zn(NO3)2·6H2O, tetrafluoroterephthalatic acid (H2tfbdc), and hexamethylenetetramine (hmt) in their respective solvent systems. Complex 1 shows a 3D pillar-layered framework with rare (3,5)-connected gra topology, while 2 has a 1D zigzag chain structure, with the interchain hydrogen-bonding interactions resulting in the formation of a 3D network. The results reveal that the coordinated-solvent plays a subtle and important role in the assembly procedure. Photoluminescent property of the complexes has also been investigated.Two new coordination polymers, [Zn2(tfbdc)2(DMF)2(EtOH)]n with rare (3,5)-connected gra topology and [Zn(tfbdc)(MeOH)4]n with 1D zigzag chain, have been obtained via coordinated-solvent effect and the two complexes display fluorescent properties.Display Omitted► Two Zinc(II) coordination Polymers have been obtained via coordinated-solvent effect. ► Complex 1 exhibits 3D framework with rare (3,5)-connected gra topology. ► Complex 2 shows 1D zigzag chain and further 3D hydrogen-bonding structure. ► Coordinated-solvent plays a subtle role in distinct architecture of both complexes. ► Complex 1 exhibits 3D framework with rare (3,5)-connected gra topology; Complex 2 shows 1D zigzag chain and further 3D hydrogen-bonding structure.
Keywords: Zinc-organic frameworks; (3,5)-connected gra net; Solvent effect; Tetrafluoroterephthalate; Photoluminescence;

A sulfonamidoquinoline-derived Zn2+ fluorescent sensor with 1:1 Zn2+ binding stoichiometry by Changli Zhang; Yuming Zhang; Yuncong Chen; Zhijun Xie; Zhipeng Liu; Xindian Dong; Weijiang He; Chen Shen; Zijian Guo (304-307).
The integration of bis(pyridin-2-ylmethyl)amine (BPA) with 8-sulfonamidoquinoline (SQ) resulted in a new fluorescent Zn2+ sensor of 1:1 binding stoichiometry. The synergic Zn2+ coordination of BPA and SQ motifs provides the sensor the advantage over TSQ and its analogues in discriminating mobile Zn2+ from the bound Zn2+ of unoccupied coordination sites in living systems. Its pH-independent Zn2+-enhanced emission in physiological condition and cell permeability make it an effective intracellular Zn2+ imaging agent. This sensor profits also from its confirmed Golgi-preferential affinity, and its pH-independent Zn2+ response in physiological pH range provides it the advantages over other xanthenone-based sensors.The BPA incorporation in 8-sulfonamidoquinoline provides a novel Zn2+ fluorescent sensor BPSQ with 1:1 Zn2+ binding stoichiometry. It possesses the pH-independent sensing behavior, cell permeability and the higher ability than TSQ in discriminating the mobile Zn2+ from those of unoccupied coordination sites in biological systems.Display Omitted► A new sulfonamidoquinoline-based Zn2+ fluorescent sensor. ► The 1:1 Zn2+ binding stoichiometry other than 2:1 of normal TSQ analogues. ► The intracellular Zn2+ imaging ability and Golgi preference. ► Reducing the interference of the partially coordinated Zn2+ with the mobile Zn2+.
Keywords: Sulfonamidoquinoline; Zinc; Fluorescent sensor; Imaging;

Two new chiral pyridyl pyrazine ligands reacted with silver(I) ion to form two different polymers—one with an achiral trigonal bipyramidal silver(I) chain and the other a chiral tetrahedral chain with an interesting repeating Λ,Δ-silver(I) configuration.Display Omitted► Two new chiral silver coordination polymers based on chiral pyridyl pyrazine ligands. ► One polymer is a directional linear polymer. ► Another polymer has a non-directional zigzag form with a repeating Λ,Δ-configuration. ► Circular dichroism spectra of the two polymers are compared.
Keywords: Coordination polymer; Chiral polymer; Chiral pyridyl ligand; Chiral pyrazine ligand; Silver complex;

The first (tricarbollide)rhodium halide complexes by Dmitry A. Loginov; Zoya A. Starikova; Pavel V. Petrovskii; Josef Holub; Alexander R. Kudinov (313-315).
Reactions of (η-1-tBuNH-1,7,9-C3B8H10)Rh(cod) with Br2 or I2 give complexes [(η-1-tBuNH-1,7,9-C3B8H10)RhX2]2 (X = Br ( 2a ), I ( 2b )). Reaction of 2b with TlBF4 affords cation [(η-1-tBuNH-1,7,9-C3B8H10)2Rh2(μ-I)3]+ ( 3 ). Complex 2a reacts with Tl[Tl(η-7,8-C2B9H11)] giving the bis(carborane) complex (η-1-tBuNH-1,7,9-C3B8H10)Rh(η-7,8-C2B9H11) ( 4 ). Structures of 2a,b were determined by X-ray diffraction.]The first (tricarbollide)rhodium halide complexes [(η-1-tBuNH-1,7,9-C3B8H10)RhX2]2 (X = Br,I) were prepared and structurally characterized. Their utility as synthons of the rhodacarborane fragment [(η-1-tBuNH-1,7,9-C3B8H10)Rh]2+ was demonstrated.Display Omitted► Synthesis of the first (tricarbollide)rhodium halide complexes. ► Halide complexes as synthons of rhodacarborane fragments. ► (Tricarbollide)rhodium halide complexes have dimeric structure.
Keywords: Boranes; Metallacarboranes; Rhodium; Tricarbollide;

Synthesis, structure and properties of a novel iridium(III) pyrimidine complex by Zhi-Qiang Wang; Chen Xu; Xin-Ming Dong; Ya-Peng Zhang; Xin-Qi Hao; Jun-Fang Gong; Mao-Ping Song; Bao-Ming Ji (316-319).
An iridium(III) pyrimidine complex Ir(NDMP)2acac (NDMP = 2-(2-naphthyl)-4,6-dimethylpyrimidine, acac = acetylacetonate) was synthesized and characterized by 1H NMR, 13C NMR, MALDI-TOF mass spectrometry and elemental analysis. An unexpected mononuclear complex Ir(NDMP)2(Cl)(H2O) was obtained in the process of preparing the Cl-bridged dimer [Ir(NDMP)2Cl]2. The crystal structures of these complexes were determined by X-ray single crystal diffraction and contrastively studied. The photoluminescence spectrum of Ir(NDMP)2acac exhibits a yellow emission at 560 nm. The HOMO and LUMO energy levels of Ir(NDMP)2acac were calculated to be − 5.14 eV and − 2.80 eV respectively.A new cyclometalated iridium(III) pyrimidine complex Ir(NDMP)2acac was synthesized and characterized. A mononuclear complex Ir(NDMP)2(Cl)(H2O) was found in the synthesis process of the Cl-bridged dimer [Ir(NDMP)2Cl]2, and the target product Ir(NDMP)2acac can be prepared from either Ir(NDMP)2(Cl)(H2O) or [Ir(NDMP)2Cl]2. (NDMP)2acac is a promising yellow phosphorescent material for OLED.Display Omitted► A new cyclometalated iridium(III) pyrimidine complex Ir(NDMP)2acac was synthesized. ► Ir(NDMP)2acac was synthesized from either [Ir(NDMP)2Cl]2 or Ir(NDMP)2(Cl)(H2O). ► The crystal structures of all these iridium(III) complexes were studied. ► Ir(NDMP)2acac is a promising phosphorescent material for OLEDs.
Keywords: Iridium(III) complexes; Phosphorescence; Cl-bridged dimer; Pyrimidine; Crystal structures;

Two new 3D lanthanide metal-organic frameworks constructed from nitrilotriacetate and oxalate ligands by Qing-Feng Yang; Xiao-Bing Cui; Yan Chen; Zheng Wang; Jie-Hui Yu; Ji-Qing Xu; Tie-Gang Wang (320-323).
Two isomorphous three-dimensional lanthanide metal-organic frameworks, K[Ln2(NTA)(ox)2(H2O)2]·3H2O (Ln = Pr (1) and Gd (2), NTA = nitrilotriacetate, ox = oxalate) have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis (TGA) and magnetic analyses. The 3D frameworks of compounds 1 and 2 possess three topologically nonequivalent 4-connected nodes synchronously and exhibit unprecedented (65∙ 8)(43∙ 63)(4∙65) topologies. Variable-temperature magnetic susceptibility measurements for complexes 1 and 2 indicate there exist antiferromagnetic interactions between magnetic centers.Two isomorphous three-dimensional lanthanide metal-organic frameworks have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis (TGA) and magnetic analyses. The 3D frameworks of compounds 1 and 2 possess three topologically nonequivalent 4-connected nodes synchronously and exhibit unprecedented (65∙ 8)(43∙ 63)(4∙65) topologies.Display Omitted► Two 3D metal-organic frameworks containing NTA and ox ligands were synthesized. ► The frameworks possess three nonequivalent 4-connected nodes synchronously. ► The 3D frameworks exhibit unprecedented (65∙8)(43∙63)(4∙65) topologies.
Keywords: Lanthanide; Metal-organic frameworks; Topology; Magnetic analyses;

Two novel 2D monovacant Keggin phosphotungstate 3d–4f heterometallic derivatives [Cu(en)2]2H6 [Ce(α-PW11O39)2]·8H2O (1) and [Cu(dap)2(H2O)][Cu(dap)2]4.5[Dy(α-PW11O39)2]·4H2O (2) have been hydrothermally synthesized and structurally characterized.Display Omitted► 2D organic-inorganic hybrid 3d-4f heterometallic Keggin phosphotungstates. ► 2D 4-connected topological 3d-4f Keggin phosphotungstate. ► 2D 5-connected topological 3d-4f Keggin phosphotungstate. ► photoluminescent 3d-4f heterometallic polyoxometalate. ► This finding will spur the exploration on 3d-4f heterometallic polyoxometalates.
Keywords: Polyoxometalate; Phosphotungstate; 3d–4f metal; Lacunary Keggin structure;

Cyclic voltammetry and spectroelectrochemistry of a novel manganese phthalocyanine substituted with hexynyl groups by Damien Quinton; Edith Antunes; Sophie Griveau; Tebello Nyokong; Fethi Bedioui (330-332).
We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine ( 3 ), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).The synthesis of a new manganese phthalocyanine complex, Mn tetrakis(5-hexyn-oxy)phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization via “click” chemistry reaction is described.Display Omitted► Mn tetrakis(5-hexyn-oxy) phthalocyanine is synthesized for the first time. ► The complex has possible use in “click” chemistry reaction. ► Reduction to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. ► Further reduction results in the formation of Mn(II)Pc(−3).
Keywords: Manganese phthalocyanine; Cyclic voltammetry; Alkyne; Spectroelectrochemistry;

A diamond metal–organic framework with in situ generated 1H-tetrazolate-5-butyric acid ligand: Crystal structure, photoluminescence and high thermal stability by Mei-Feng Wu; Gang Xu; Fa-Kun Zheng; Zhi-Fa Liu; Shuai-Hua Wang; Guo-Cong Guo; Jin-Shun Huang (333-336).
Hydrothermal reaction of diethyl 2-(2-cyanoethyl) malonate, ZnCl2, NaN3 and NaOH yielded a new 1H-tetrazolate-5-butyrate coordination polymer, [Zn(tzb)]n (1) (H2tzb = 1H-tetrazolate-5-butyric acid), which presents a 3-D noninterpenetrating diamond network. The in situ generated tzb2− ligand adopts a μ4-bridging mode with carboxylate group in a synanti fashion and tetrazolate group in a 1,4-N manner. Polymer 1 exhibits a weak second-order nonlinear optical coefficient about 0.5 times that of potassium dihydrogen phosphate (KDP), and also displays strong blue photoluminescence at room temperature and a high thermal stability up to 400 °C.The first coordination polymer based on the bifunctional ligand 1H-tetrazolate-5-butyric acid (H2tzb), which presents a 3-D diamond network, was obtained by in situ ligand synthesis reactions from the organic precursor of diethyl 2-(2-cyanoethyl) malonate under hydrothermal condition.Display Omitted► The first polymer based on 1H-tetrazolate-5-butyric acid ligand. ► The acentric polymer exhibiting a diamond network and nonlinear optical effect. ► A good candidate for efficient blue emission materials. ► A high thermal stability up to 400 °C.
Keywords: 1H-tetrazolate-5-butyric acid; Diamond topology; Photoluminescence; Thermal stability;

Structural features and synthetic strategies of iron clusters, wheels and cages of nuclearities from 6 to 64 are discussed. Synthetic methodologies are categorized in a few groups. Magnetic behaviours of the polynuclear iron species are also highlighted.Structural features and synthetic strategies of iron clusters, wheels and cages of nuclearities from 6 to 64 are discussed. Synthetic methodologies are categorized in a few groups. Magnetic behaviours of the polynuclear iron species are also highlighted.Display Omitted► The polynuclear iron compounds act as Single Molecule Magnets (SMMs). ► These sometimes mimic the active sites of different biomolecules. ► The syntheses and structures are of utmost importance to chemists and biologists.
Keywords: Iron clusters; Wheels and cages; Syntheses; Structures; Magnetic properties;