Inorganic Chemistry Communications (v.37, #C)

Contents List (iii-xvi).

Solvothermal reactions of Cd(II) salts with biphenyl-3,4′,5-tricarboxylic acid (H3L) and melamine (MA) afford a new coordination polymer, namely [Cd3(L)2(MA)2(H2O)2]n (1). Single crystal X-ray analysis reveals that compound 1 displays a new 2D → 3D polythreaded motif directed by intermolecular hydrogen bonds, in which large opened windows of each (3,6)-connected layer are threaded by two dangling MA molecules from adjacent layers in the opposite direction. In addition, the luminescent property of 1 was also investigated in the solid state at room temperature.Presented here is a new 2D → 3D polythreaded framework directed by intermolecular hydrogen bonds, in which large opened windows of each (3,6)-connected layer are threaded by two dangling MA molecules of two adjacent layers from two opposite directions.Display Omitted
Keywords: Coordination polymer; Solvothermal reaction; Polythreading; Luminescence;

Geometry and bonding energy analysis of uranium(VI) nitride complex [NU{N(CH2CH2NSiMe3)3}] were investigated with the DFT, DFT-D3 and DFT-D3(BJ) methods using density functionals (BLYP, BP86, PW91, PBE, revPBE and TPSS). The BLYP functional yields a UN bond distance of 1.788 Å for the model complex [NU{N(CH2CH2NSiMe3)3}] which is in close agreement with the experimental value of the UN bond distance of 1.799(7) Å for [NU{N(CH2CH2NSiiPr3)3}]. The calculated Mayer bond order (2.95) and Gopinathan–Jug bond order (3.18) indicate that the U―N bond in this complex is essentially UN triple bonds. The electrostatic interaction is significantly smaller than the covalent bonding. The bond dissociation energy (BDE) is largest for the functional PBE and smallest for the functional TPSS. The DFT-D3 dispersion corrections are 5.3 kcal/mol (BLYP) and 5.0 kcal/mol (TPSS).Geometry and bonding energy analysis of uranium(VI) nitride complex [NU{N(CH2CH2NSiMe3)3}] were investigated with the DFT, DFT-D3 and DFT-D3(BJ) methods using density functionals. The BLYP functional yields better geometry. The orbital interaction ΔEorb is larger than the electrostatic interaction ΔEelstat; the U―N bond has a degree of covalent character between 61.6%.Display Omitted
Keywords: Uranium; Nitride; Bonding; DFT-D3; Noncovalent interactions;

Two sandwich-like frameworks with Ag(I) and mixed flexible ligands, {[Ag2(H2O)2(bpp)2](oba)·4H2O} n (1) and {[Ag2(bpp)2](heda)·8H2O} n (2) (bpp = 1,3-bis(4-pyridyl)propane, H2oba = 4, 4′-oxybis(benzoic acid), H2heda = trans-3-hexenedioic acid), have been synthesized and characterized. In 1, the bpp ligands bridge the Ag(I) ions into 1D sinusoidal chains of [Ag(bpp)] n n+, which are further linked into the cation layer of [Ag2(H2O)2(bpp)2] n 2n+ by Ag⋯π and Ag⋯Ag interactions. The noncoordinated oba2 − serves as template driving surrounding water molecules to aggregate into the anionic layer of [(oba)·4H2O] n 2n. In 2, the similar [Ag2(bpp)2] n 2n+ cationic layer is based on Ag⋯π interactions. The heda2 − and surrounding water molecules construct another 2D layer of [(heda)·8H2O] n 2n. Hydrogen bonds make the cationic and anionic layers into sandwich-like frameworks. Interestingly, 1D T5(1) water tapes with cyclic vertex-sharing pentamer cluster units and discrete water octamers with a boat-shaped hexamer were observed in 1 and 2, respectively. The novel water tape and discrete water octamer with a boat-shaped hexamer are different from water clusters described in previous reports. The luminescent behaviors and thermogravimetric analysis of 1 and 2 have been also discussed.Two sandwich-like Ag(I) frameworks have been synthesized and X-ray crystallography shows that they encapsulate a 1D T5(1) water tape and a discrete octamer water cluster with a boat-shaped hexamer, respectively.Display Omitted
Keywords: Sandwich; Water cluster; Boat-shaped hexamer;

Two new coordination polymers, [Cd(L1 )2(H2O)2]n (1) and [Zn3(L1 )2(pdc)2]n (2), have been obtained on the basis of new-developed tetrazolate ligand 5-benzoimidazoyltetrazolate (L1 ) in the presence of auxiliary ligand pyridine-2,5-dicarboxylic acid (H2pdc). The coordination chemistry of L1 and the effect of ancillary ligand H2pdc have been discussed. Both compounds were characterized by IR, CHN, TGA, and PXRD, and their structures were determined by X-ray crystallography. Their solid state luminescent properties were also investigated.Two new coordination polymers, [Cd(L1 )2(H2O)2]n (1) and [Zn3(L1 )2(pdc)2]n (2), have been obtained on the basis of new-developed tetrazolate ligand 5-benzoimidazoyltetrazolate (L1 ) in the presence of auxiliary ligand pyridine-2,5-dicarboxylic acid (H2pdc). The coordination chemistry of L1 and the effect of H2pdc have been investigated. Both compounds were characterized by IR, CHN, TGA, and PXRD, and their structures were determined by X-ray crystallography. The solid state luminescent properties were also investigated.Display Omitted
Keywords: In-situ synthesis; Tetrazolate; Luminescence; 1-Cyanobenzoimidazole;

The solvothermal reactions of 3,5-bis(trifluoromethyl)benzoic acid (HL) and 2,2′-bipyridine (bipy) with the corresponding metal salts afforded two novel 3d–4f tetranuclear complexes M2Dy2(L)10(bipy)2 (M = Mn 1, Cu 2), which have been characterized by single-crystal X-ray diffraction, infrared spectroscopy, element analyses, powder X-ray diffraction and thermal gravimetric analyses. Complexes 1 crystallizes in the triclinic space group P-1, and the completely deprotonated L ligands possess μ 2: η 1, η 1 and μ 2: η 2, η 1 coordination modes to bridge adjacent metal ions which further connect into 2D layers by hydrogen bonds. Complex 2 crystallizes in the distinct monoclinic space group P21/c, and adjacent metal ions were linked by L ligands with the same coordinated patterns with 1, and supramolecular sheets were formed in the ab plane. Dynamic magnetic susceptibility studies reveal slow magnetic relaxation processes for 2, suggesting SMM type behavior.Two novel 3d–4f tetranuclear complexes based on 3,5-bis(trifluoromethyl)benzoic acid have been solvothermal synthesized and characterized. They both exhibit tetranuclear structure feature, whereas crystallize in different space group and have various magnetic behavior. Complex 2 shows slow magnetic relaxation processes.Display Omitted
Keywords: Crystal structures; 3d–4f; Tetranuclear; Magnetic properties;

A bis-pyridine unit containing azobenzene chemosensor for Cu2 + ion is designed and synthesized with good yield. The structure of the receptor I is determined by FT-IR, 1H NMR, 13C NMR, ESI-MS and single crystal XRD. The receptor I is constructed on the basis of internal charge transfer (ICT) mechanism with bis-pyridine unit acting as the binding part for Cu2 + ion. In solution, the proposed receptor I produces a cation induced 120 nm blue shift for Cu2 + ion from 457 nm to 337 nm with remarkable colour change from red to colourless. Whereas no significant colour change is observed upon addition of other metal ions in aqueous HEPES buffer (pH 7.0). Moreover, spectroscopic studies confirm the formation of 1: 1 stoichiometry between the receptor I and Cu2 + ion with an association constant of ca. 1.45 × 106  M− 1. The receptor I is highly specific to Cu2 + ions in aqueous solution attributed to the rational design of the molecular structure.A new bis-pyridine containing azobenzene receptor I was designed, synthesized and characterized. Receptor I was found to be an excellent chemosensor for Cu2 + ions than the other tested metal ions. The strong binding affinity and remarkable colour change with Cu2 + ion make the receptor I ideal for sensor applications.Display Omitted
Keywords: Azo dye; Chemosensor; Copper (II) ion; Internal charge transfer;

Simple synthetic procedure, reaction of Os[P(C6H5)3]2(CO)2Cl2 with 2-phenylpyridine (or other similar N∩CH chelating ligands) in boiling 2-(2-ethoxyethoxy)ethanol solution leads to Os[P(C6H5)3]2(CO)(N∩C)Cl complexes. Structures of the obtained species have been elucidated by means of 31P NMR and FT-IR techniques as well as elemental analysis data. The UV–vis absorption and emission properties of the newly synthesized complexes reveal the MLCT character of their lowest singlet and triplet excited states.Simple reaction of K2OsCl6 with P(C6H5)3 performed in refluxing DMF solution leads to quantitative formation of trans-cis-cis-Os[P(C6H5)3]2(CO)2Cl2. In reactions with different bidentate N∩CH ligands the synthesized Os[P(C6H5)3]2(CO)2Cl2 precursor can be further converted to luminescent Os[P(C6H5)3]2(CO)(N∩C)Cl chelates.Display Omitted
Keywords: Osmium carbonyls; Chelating cyclometalated base ligands; 31P NMR; FT-IR and UV–vis spectroscopy;

Four isostructural lanthanide metal–organic frameworks (Ln-MOFs), [Ln2(BPDC)(BDC)2(H2O)2] n (Ln = Gd (1), Dy (2), Ho (3), Er (4)) have been synthesized via a mixed ligand approach based on 2,2′-bipyridine-3,3′-dicarboxylic acid (H2BPDC) and 1,4-benzenedicarboxylic acid (H2BDC) under hydrothermal conditions. TGA reveal the high thermal stability of these compounds. The magnetic properties of 1–4 have been studied. Weak antiferromagnetic interaction exists between Gd3 + ions in 1 and the maximum magnetic entropy change of 1 reaches 10.2 J kg− 1  K− 1 (22.9 mJ cm− 3  K− 1) for H  = 7 T. Luminescent measurement shows the characteristic sharp emission bands of Dy3 + ions in 2.Four lanthanide metal–organic frameworks [Ln2(BPDC)(BDC)2(H2O)2]n (Ln = Gd (1), Dy (2), Ho (3), Er (4)) were synthesized and characterized. 1 exhibits weak antiferromagnetic interaction and its maximum magnetic entropy change reaches 10.2 J kg− 1  K− 1 at 2 K. 2 shows the typical luminescence of Dy3 + ions.Display Omitted
Keywords: Ln-MOFs; Magnetic property; Magnetocaloric effect; Luminescence;

New mononuclear copper(II) complex based on a salen derivative ligand with an unusual coordination and its catecholase activity by Tiago Pacheco Camargo; Rosely A. Peralta; Raphaell Moreira; Eduardo E. Castellano; Adailton J. Bortoluzzi; Ademir Neves (34-38).
The new mononuclear copper(II) complex [CuII(H2LDA)(ClO4)](ClO4) (1) ([H2LDA =  N,N′-[bis-(2-hydroxy-3-formyl-5-methylbenzyl)(dimethyl)]-ethylenediamine]) with an unusual coordination mode of a salen derivative ligand is reported. The most interesting feature of 1 is that the ligand is doubly protonated and presents significant intermolecular π-stacking interactions, contributing to the dimer structure stabilization in the solid state and in CH3CN and methanolic solutions. The complex was characterized by X-ray crystallography and shows catecholase-like activity in the oxidation of the substrate 3,5-di-tert-butylcatechol (3,5-dtbc), with the formation of H2O2, which kinetic parameters are similar to those observed in conventional dinuclear bridged CuII complexes.This work reports on the synthesis, structure and catecholase-like activity of a new dimeric copper(II) complex which is stabilized in the solid state and in methanolic solution through π-stacking interactions.Display Omitted
Keywords: Salen derivative ligand; Copper(II) complex; π-Stacking; Catecholase;

We report a new well dispersed molybdenum–Schiff base complex covalently attached to the surface of multi-wall carbon nanotubes (MWCNTs). Nitrogen adsorption–desorption (BET) analysis of the prepared hybrid nanomaterial revealed that the textural characteristics of the support were preserved during the grafting experiments despite sequential reduction in surface area and pore volume. The prepared nanomaterial showed good performance and stability in the catalytic epoxidation of olefins with tert-butylhydroperoxide (TBHP) and cumene hydroperoxide (CHP) under mild reaction conditions.New epoxidation catalyst was prepared from immobilizing molybdenum–Schiff base complex through the mediation of aminopropylsilyl groups on the surface of multi walled carbon nanotubes (MWCNTs).Display Omitted
Keywords: Carbon nanotube; Molybdenum; Immobilization; Epoxidation;

Three new cobaloximes (ClCH2Co(dpgH)2Y (Y = pyridine, water, N-methylimidazole, dpgH = diphenylglyoximate)) have been synthesized and characterized by elemental analysis and spectral studies. The molecular structures of ClCo(dpgH)2Py and ClCH2Co(dpgH)2N-methylimidazole are described. In the packing diagram of ClCH2Co(dpgH)2N-methylimidazole, molecules are bonded through CH–π interaction with the range of distances of 2.798–3.067 Å. The axial substituents, pyridine and N-methylimidazole affect the properties of the Co center.Three new cobaloximes (ClCH2Co(dpgH)2Y (Y = pyridine, water, N-methylimidazole, dpgH = diphenylglyoximate)) have been synthesized and characterized by elemental analysis and spectral studies, and molecular structures of ClCo(dpgH)2Py and ClCH2Co(dpgH)2N-methylimidazole are described.Display Omitted
Keywords: Cobalt(III) complexes; Cobaloximes; Spectral studies; Single X-ray structure;

Two new metal coordination polymers [Cd2(ba)4(L)2]n (1) and [Zn(tda)(L)]n (2) [Hba = benzoic acid, H2tda = 2,5-thiophenedicarboxylic acid and L = 3,5-bis(benzoimidazo-1-ly)pyridine] have been successfully synthesized and structurally characterized by IR, elemental analysis, X-ray powder diffraction and X-ray single-crystal diffraction. For complex 1, two Cd(II) ions and four ba ligands form the dimetal clusters, which are further connected through the L ligands to give rise to a uninodal 3-connected hcb Shubnikov hexagonal plane net with the 63 topology. Complex 2 features the 3-connected topological net with 82  ∙ 10 topology (so-called “tongue-and groove” structure). The Zn(II) node together with the four surrounding coordinated ligands form a typical T-shaped molecular bilayer motif, which is rarely reported previously. Their X-ray powder diffraction patterns were then carried out to confirm the validity of the crystal structures. In addition, the luminescent properties of 1 and 2 are investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the two complexes.Two novel coordination polymers [Cd2(ba)4(L)2]n (1) and [Zn(tda)(L)]n (2) have been synthesized under hydrothermal conditions. Complex 1 possesses a uninodal 3-connected hcb Shubnikov hexagonal plane net with the 63 topology, while complex 2 features the 3-connected topological net with 82  ∙ 10 topology. In 2, the Zn(II) node together with the four surrounding coordinated ligands form a typical T-shaped molecular bilayer motif, which was rarely reported previously.Display Omitted
Keywords: 3,5-Bis(benzoimidazo-1-ly)pyridine; Hydrothermal synthesis; Crystal structure; Coordination polymer; Luminescence;

Two Co(II) coordination polymers, namely [Co(L1)(tp)] n (1) and [Co(L2)(Htp)(tp)0.5] n (2) (L1 = 1,3-bis(5,6-dimethylbenzimidazole)propane; L2 = 1,2-bis(5,6-dimethylbenzimidazole-1-ylmethyl)benzene; tp = terephthalate) have been synthesized and structurally characterized by single crystal X-ray diffraction. In 1, the Co(II) centers are four-coordinated and lie in nearly perfect tetrahedron coordination environment. The 2D (4, 4) layer is formed by the bridging L1 and tp ligands, which further assembles into a 3D supramolecular framework by ππ stacking interactions. In 2, the Co atoms are in distorted trigonal–bipyramidal geometry and linked by tp ligands to generate a 1D linear chain. The adjacent chains are finally extended to a 2D supramolecular layer through hydrogen-bonding interactions. In addition, fluorescence and remarkable adsorption properties for congo red dye of complexes 1 and 2 have been investigated.This work presents two Co(II) coordination polymers based on bis(5,6-dimethylbenzimidazole) ligands with different flexibility and terephthalic acid, which display a 2D (4, 4) layer and a 1D chained coordination structure. The two polymers both exhibit high adsorption capacity for congo red dye.Display Omitted
Keywords: Adsorption; Bis(5,6-dimethylbenzimidazole); Co(II) coordination polymers; Flexibility; Fluorescence;

Luminescent cis-[CoIII(en)2(RNH2)Cl]Cl2 (where RNH2  = HexnNH2, PennNH2, BuiNH2, BunNH2, PrnNH2, EtNH2, MeNH2, BznNH2) complexes exhibiting ferromagnetism with some rationalization of magneto-structural features have been synthesized. Such characteristics were verified using auxiliary RNH2 ligands. The complexes show emission (λem ~ 411 nm and τ1 ~ 3, τ2 ~ 10, τ3 ~ 0.7 ns) in fluid solutions upon excitation at λex  = 360 nm. The manifestation of luminescence is attributed due to ligand-to-metal charge transfer emissive state. Electron rich ligand permits a significant reduction in the lifetime of the prominent emitting state Co(III)–HexnNH2 (τ2  = ~ 9.5 ns) < Co(III)–MeNH2 (τ2  = ~ 12.3 ns) due to (i) destabilization of d–d mixed LMCT emitting state, and (ii) smaller HOMO–LUMO gap. The E pc  = 357–396 mV values observed for CoIII(en)2(RNH2)Cl2 + in solvents such as DMSO, water and water/PriOH shows metal-centered reduction and a simple one electron transfer process because the current function (Ipc1/2) is independent of sweep rate (50–350 mV s− 1). Importantly, cobalt(III) complex with short chain RNH2 exhibits higher saturation magnetization; M s  = 150.8 × 10− 4  μB/Co3 + than complex with long chain RNH2, in which M s  = 0.5 × 10− 4  μB/Co3 + at 298 K, this indicates the manifestation of ferromagnetic coupling in CoIII(en)2(RNH2)Cl2 + cation. In essence, the effect of RNH2 on luminescence, electrochemical and magnetic properties of cis-[CoIII(en)2(RNH2)Cl]Cl2 has been rationalized. Such correlation provides an outcome on the signature of the substituent, RNH2 moiety in cobalt(III)–alkyl amine complexes.Luminescent cis-[CoIII(en)2(RNH2)Cl]Cl2em ~411 nm; τ2 ~10-12 ns) complexes show weak ferromagnetism: Ms = 0.5-150 x 10− 4µB/Co3 + with some rationalization of magneto-structural features. Cyclic voltammetric study indicates metal-centered reduction (Epc = 357 - 396 mV) through one electron transfer.Display Omitted
Keywords: Photoluminescence; Triexponential decay models; Electrochemistry; Tafel analysis; Ferromagnetism in cobalt(III) complex;

Structure, characterization and near-infrared emission of a novel 6-connected uninodal 3D network of Nd(III) containing 2,5-thiophenedicarboxylate anion by Lippy F. Marques; Charlane C. Corrêa; Róbson Rosa da Silva; Molíria Vieira dos Santos; Sidney J.L. Ribeiro; Flávia C. Machado (66-70).
The novel coordination polymer with the formula {[Nd2(2,5-tdc)3(dmf)2(H2O)2].dmf.H2O}n (2,5-tdc2 −  = 2,5-thiophedicarboxylate anion and dmf = dimethylformamide) has been synthesized and characterized by thermal analysis (TG/DTA), vibrational spectroscopy (FTIR) and single crystal X-ray diffraction analysis (XRD). Structure analysis reveals that Nd(III) ions show dicapped trigonal prism coordination geometry. The 2,5-tdc2 − ligands connect four Nd(III) centers, adopting 1 – κ1) – (κ1 – κ1) – μ4 coordination mode, generating an interesting 6-connected uninodal 3D network. Photophysical properties were studied using diffuse reflectance spectroscopy (DR) and excitation/emission spectra. The photoluminescence data show the near infrared emission (NIR) with the characteristic 4F3/2  →  4IJ (J = 9/2, 11/2 and 13/2) transitions of Nd(III) ion, indicating that 2,5-tdc2 − is able to act as a sensitizer for emission in NIR region.A novel Nd(III) coordination polymer has been synthesized and characterized by thermal analysis (TG/DTA), vibrational spectroscopy and single crystal X-ray diffraction analysis. Structure analysis reveals Nd(III) ions in dicapped trigonal prism coordination geometry. Photophysical properties were studied using diffuse reflectance spectroscopy and excitation/emission spectra, which show the near infrared emission.Display Omitted
Keywords: Coordination polymer; 2,5-Thiophenedicarboxylic acid; Lanthanides;

The coordination polymer {[Cu3(sip)2(dpp)4]·14H2O} n (sip = 5-sulfoisophthalate, dpp = 1,3-di(4-pyridyl)propane) was synthesized and structurally characterized by single-crystal X-ray diffraction. The crystallographically distinct copper atoms represent distinct 4-connected nodes that form a novel yet very simple 4,4,4-connected (6482)2(66) topology, which resembles a hybrid of well-known diamondoid and PtS networks. Incipient one-dimensional channels containing chains of disordered water molecules occupy 26.7% of the unit cell volume. Upon removal, the coordination polymer apohost does not permit gas absorption.The coordination polymer {[Cu3(sip)2(dpp)4]·15H2O} n (sip = 5-sulfoisophthalate, dpp = 1,3-di(4-pyridyl)propane) was synthesized. The copper atoms represent 4-connected nodes that form a novel 4-connected trinodal (6482)2(66) topology that resembles a hybrid of diamondoid and PtS networks. Channels containing chains of disordered water molecules occupy 26.7% of the unit cell volume.Display Omitted
Keywords: Coordination polymer; Copper; Crystal structure; Hydrothermal;

A new mixed metal borate of BaPb[B5O9(OH)]·H2O with acentric structure by Han-Qing Wu; Huan He; Bai-Fei Yang; Guo-Yu Yang (77-79).
A new mixed matel borate, BaPb[B5O9(OH)]·H2O (1), with an acentric structure has been successfully made under hydrothermal conditions. A single-crystal X-ray structural analysis shows that 1 crystallizes in the monoclinic space group Cc (No. 9) with a  = 11.3194(6) Å, b  = 6.6265(3) Å, c  = 12.9256(8) Å, β  = 115.065(7)°, and Z  = 4. Compound 1 has a layered structure with 9-membered ring (MR) windows, where the Pb2 + cations locate, while the Ba2 + cations site in the channels formed by H-bonding interactions of adjacent layers. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits SHG efficiency approximately 2.2 times that of KH2PO4 (KDP) and phase-matching. Also it has a UV cutoff edge below 200 nm.A new acentric mixed metal borate BaPb[B5O9(OH)]·H2O has been successfully made under hydrothermal conditions, showing good second-harmonic generation efficiency approximately 2.2 times that of KH2PO4.Display Omitted
Keywords: Borate; Cluster; Nonlinear optical; Hydrothermal syntheses; Crystal structure;

Anionic cyclometallated iridium(III) complexes containing substituted bivalent ortho-hydroquinones by Elisabeta Ildyko Szerb; Andreea Ionescu; Nicolas Godbert; Yogesh Jivajirao Yadav; Anna Maria Talarico; Mauro Ghedini (80-83).
The straightforward synthesis, redox and photophysical properties of a series of Ir(III) complexes of general formula [(ppy)Ir(O^O)]NBu4, ( 1 3 ) where ppy is 2-phenylpyridine and O^O are tetrachlorocatecholate ( 1 ), tetrabromocatecholate ( 2 ) or alizarinate ( 3 ) in their dianionic forms, are reported.The synthesis and structural characterisations of new Ir(III) anionic complexes containing bivalent functionalized cathecolate ligands are described. An intensive electrochemical investigation showed the high stability of the first oxidation process. Remarkably, the complex containing the alizarine dye is one of the few Ir(III) complexes reported so far that has strong absorption extending as far as 700 nm. The complexes described herein give access to a pool of similar compounds within the large class of ortho-hydroquinone based dyes, highly interesting for electrochromic, redox switchable and sensor materials.Display Omitted
Keywords: Ir(III) anionic complexes; Synthesis; Photophysics; Electrochemistry;

Temperature-dependent crystal structures and unusual dielectric property in [Me2NH2]2[Ni(mnt)2] by Ping-Ping Shi; Su-Wen Sun; Ming-Liang Liu; Li-Hui Kong; Qiong Ye (84-88).
The title compound bis(dimethylammonium) bis(dicyanoethene-1,2-dithiolato)-nickel (II) undergoes a reversible dielectric transition occurring at about 260 K. The variable-temperature X-ray structural determinations reveal that both phases are monoclinic, space group C2/c with a  = 16.383(3), b  = 9.521(5), c  = 13.631(3) Å, β  = 118.28(3)°, V  = 1872.5(8) Å3 at the room temperature (293 K), and with a  = 15.885(5), b  = 9.418(0), c  = 13.771(3) Å, β  = 116.89(3)°, V  = 1837.4(8) Å3 at the low temperature (93 K). The [Ni(mnt)2]2 − anions form a non-uniform stacking pattern and interact with the [Me2NH2]+ cations by N–H∙∙∙S, N–H∙∙∙N hydrogen bonds, for the two phases. With temperature increasing, the cations and anions are shifting and thus result in the significant changes of the hydrogen bonds. The effect of these shifts is reflected in the dielectric behavior of the [Me2NH2]2[Ni(mnt)2] salt (mnt2 −  = maleonitriledithiolate).The novel complex bis(dimethylammonium) bis(dicyanoethene-1,2-dithiolato)-nickel (II), [Me2NH2]2[Ni(mnt)2], has been synthesized and investigated its temperature-dependent crystal structures and dielectric property. With temperature increasing from 93 K to 293 K, both the cations and anions are shifting in the stack and result in the significant changes of the hydrogen bonds, however, with no change in the space group. These structural changes are reflected in the reversible dielectric transition.Display Omitted
Keywords: X-ray structure; Order–disorder; Shift; Dielectric transition;

Aluminium chloride catalyses hydrolysis of 2-(5-methylthiazol-2-yliminomethyl)phenol (1). This reaction can be specifically used for detection of Al3 + ions in the presence of various other ions from the characteristic emission at 446 nm (λex  = 365 nm). On the other hand selective emission of 2-(5-methylthiazol-2-yliminomethyl)phenol on interaction with zinc ions at 490 nm (λex  = 365 nm) can be used to detect Zn2 + ions. The role of other ions such as Cu2 +, Hg2 +, and Sn2 + in the detections are discussed.The 2-(5-methylthiazol-2-yliminomethyl)phenol (1) can be used to detect Al3 + and Zn2 + ions in the presence of various metal ions.Display Omitted
Keywords: Catalytic hydrolysis; Schiff-base; Al3 + ions; Zn2 + ions; Fluorescence;

Amine-directed structural studies of four zinc metal-organic frameworks based on a novel phosphonocarboxylate ligand by Wenyan Dan; Xiaofeng Liu; Mingli Deng; Yun ling; Zhenxia Chen; Yaming Zhou (93-96).
A novel phosphonocarboxylic ligand, 4′-phosphonobiphenyl-3,5-dicarboxylic acid (H4pbpdc), was synthesized to construct 4 zinc compounds, namely, {[Zn3(pbpdc)2·2R}n (R = C5H12N for 1, C4H10N for 2 and C6H16N for 3) and {[Zn2pbpdc]·C6H18N3}n(4), which were characterized by X-ray crystallography, elemental analysis, FTIR and TG. Structures 1  ~  3 have the same 3-dimensional (3-D) frameworks with point symbol of {4.6.73.8}2{42.6.72.8}2{42.62.7.8}2{42.62.72}. Structure 4 is constructed from a 6-connected metallic cluster and 3-connected phosphonocarboxylic building units resulting in a topology of flu-3,6-C2/c. The luminescent properties of compounds 1  ~  4 and organic ligand were studied.Organic amines were used to direct 4 distinct zinc metal-organic frameworks based on a novel phosphonocarboxylate ligand. They have 2 topologies of {4.6.73.8}2{42.6.72.8}2{42.62.7.8}2{42.62.72} and flu-3,6-C2/c, respectively. The roles of organic amines in the formation of frameworks were discussed.Display Omitted
Keywords: Metal phosphonocarboxylate; Synthesis; Topology; Luminescence;

Novel zinc phthalocyanine (ZnPc) containing symmetrically eight triaza-tetraoxa macrobicycles on peripheral positions has been synthesized in a multistep reaction sequence. The cyclotetramerization reaction was accomplished with 4,5-bis[2-(4,7,13,16-tetraoxa-1,10,22-triazabicyclo[8.8.7]pentacosane-22-yl)ethylthio]phthalonitrile (6) which was prepared by the reaction of 1,2-bis(2-iodoethoxy)-4,5-dicyanobenzene (5) and 4,7,13,16-tetraoxa-1,10,22-triazabicyclo[8.8.7]pentacosane (4). The novel compounds were characterized by a combination of elemental analysis, 1H and 13C NMR, IR, UV–vis and MS spectral data.New zinc phthalocyanine (ZnPc) has been prepared containing symmetrically eight triaza-tetraoxa macrobicycles on peripheral positions has been prepared by a cyclotetramerization reaction of macrobicyclic dinitrile (6).Display Omitted
Keywords: Zinc(II) phthalocyanine; Macrobicycles; High dilution; Template effect; Detosylation; Nitrogen-oxygen mixed donor;

Heptanuclear cobalt(II) dicubane compounds with single-molecule magnet behavior by Guilherme P. Guedes; Stéphane Soriano; Nadia M. Comerlato; Nivaldo L. Speziali; Miguel A. Novak; Maria G.F. Vaz (101-105).
The reaction between the tetranuclear compound [Co4(tta)4(OMe)4(MeOH)4] (tta = 4,4,4-trifluoro-1-thienoyl-2,4-butanedionate) and isopropanol or n-butanol leads to two heptanuclear compounds with general molecular formula [Co7(OH)8(tta)6(ROH)6]·ROH (R = isopropyl, for 1 or n-butyl, for 2). The crystal structures of both heptamers consist of two cubane-like units linked through one shared cobalt(II) ion vertex. The reaction leads to the replacement of precursor methoxide bridges by hydroxo in the heptanuclear compounds, which connect the internal metal ion to the six external ones. The magnetic properties revealed moderate ferromagnetic interactions among the cobalt(II) ions. Furthermore, ac magnetic susceptibility measurements confirm that these compounds are new examples of single-molecule magnets (SMM) containing cobalt(II) ions, with an energy barrier for magnetization reversal of 22 K and 21 K, respectively for 1 and 2.The reaction between isopropanol or n-butanol and the tetranuclear precursor [Co4(tta)4(OMe)4(MeOH)4] (tta = 4,4,4-trifluoro-1-thienoyl-2,4-butanedionate) leads to two heptanuclear compounds with general molecular formula [Co7(OH)8(tta)6(ROH)6]·ROH (R = isopropyl or n-butyl). Moderate ferromagnetic interactions are present in both compounds. Ac magnetic measurements revealed that these compounds behave as single-molecule magnets at low temperatures.Display Omitted
Keywords: Molecular magnetism; Cobalt(II); Single-molecule magnets; β-Diketonate;

Small change, big red shift: syntheses, structure and photoluminescence of Cu2Br2(Ph3P)2py2 (py = pyridine, 4-vinylpyridine) by Daniel Volz; Martin Nieger; Jana Friedrichs; Thomas Baumann; Stefan Bräse (106-109).
The search for efficient, luminescent metal complexes for optoelectronic devices raised the interest for emissive Cu(I) compounds. Cu(I)-complexes of the type [Cu2X2(PR3)2(py)2] (py = pyridine derivative, X = Cl, Br, I) usually are efficient, blue-emitting compounds that can potentially be used as new emitter materials in organic light-emitting diodes. Aside from photophysical requirements, the introduction of functional groups is often necessary to enable processing and stabilization, e.g. by cross-linking or polymerization. Using 4-vinylpyridine instead of pyridine to enable crosslinking during device fabrication, a structurally similar complex with different photophysical properties is obtained: a bathochromic shift of over 100 nm occurs, while the photoluminescence quantum efficiency is drastically decreased. DFT-calculations, X-ray-diffraction and photoluminescence spectroscopy were used to compare Cu2Br2(Ph3P)2(pyridine)2 and Cu2Br2(Ph3P)2(4-vinylpyridine)2. The structural differences regarding the core unit, Cu2Br2P2N2, are only small, but the π-system of the pyridine ligand is enlarged by the vinyl group leading to a significant red-shift of the emission wavelength.Cu(I)-complexes of the type [Cu2X2(PR3)2(pyridine)2] are usually efficient blue emitters. Using 4-vinylpyridine instead, the photophysical properties change drastically. While the PLQY is substantially lower, the emission is red-shifted. The reason for this was found to be an extension of the LUMO, which opens up new quenching paths.Display Omitted
Keywords: Copper complex; Luminescence; Bathochromic shift; Singlet harvesting; Organometallic compound;

Rectangular bimetallic diorganotin macrocycle obtained through a combination of metallosupramolecular chemistry with imine bond formation by Nelly González-Rivas; Erick Cuevas-Yañez; Victor Barba; Hiram I. Beltran; Horacio Reyes (110-113).
Herein it is presented a combination of metallosupramolecular chemistry with imine bond formation in the one pot strategies, this is a two step multi-condensation procedure to prepare a bis-diorganotin(IV) macrocycle. First, the 2:1 condensation reaction of 3-aminobenzoic acid (1) with di-n-butyltin(IV) oxide in acetonitrile led a diorganotin(IV) building block. This followed a second step through the [2 + 2] condensation reaction with terephthalaldehyde (2) thus allowing the synthesis of a rectangular shaped 38-membered bis-iminic-diorganotin macrocycle (3). X-ray analysis of the macrocycle co-crystal with 1,3,5-trimethyltrioxane (paraldehyde) reveals a highly symmetric binuclear rectangular macrocyclic compound with approximate dimensions of 17.4 Å (length) × 14.0 Å (width).Combining metallosupramolecular chemistry with imine bond formation in a one pot two step multi-condensation procedure allows the preparation of a rectangle shaped bis-diorganotin(IV) macrocycleDisplay Omitted
Keywords: Diorganotin (IV) macrocycles; Condensation reactions; Supramolecular architectures;

Three novel mixed-ligand complexes using pyrazolone derivative (4-chloro-benzylidene-4-aminoantipyrine) as primary ligand and l-methionine as co-ligand, were synthesized and characterized by physico-chemical analytical techniques. The DNA interaction of these complexes was investigated by electronic absorption spectroscopy, viscosity, cyclic voltammetry and gel electrophoresis measurements. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens.The synthesized effective DNA targeting amino acid metal chelates are valuable in designing novel agents for targeting tumor cells as well as setting the stage for the synthesis of metal nuclease drugs for clinical applications.Display Omitted
Keywords: Mixed-ligand complexes; DNA interaction; Gel electrophoresis; Antimicrobial agents;

Phosphorescent iridium(III) carbodithioate complex for the detection of Hg2 + and acetonitrile by Bihai Tong; Peng Ma; Man Zhang; Yuanyuan Liu; Qunying Mei; Qian-Feng Zhang (121-126).
A cyclometalated iridium(III) complex Ir(dpci)2(cbd) (Ir1, dpciH = 3, 4-diphenylcinnoline, cbd = N-carbazolylcarbodithioate) has been prepared and confirmed by 1H NMR, 13C NMR, MS, and crystal data. Ir1 could be used as a phosphorescent chemosensor for Hg2 + and acetonitrile (ACN). Upon addition of aqueous Hg2 +, the ACN solution of Ir1 gave a visual color change and significant phosphorescent enhancing (130-fold) at 580 nm (OFF–ON). Ir1 has been developed as an AND logic gate with Hg2 + and ACN as inputs. The dissociation of Ir1 and coordination with ACN are response for the sensor process.A cyclometalated iridium(III) complex Ir(dpci)2(cbd) (Ir1) has been prepared and confirmed. Ir1 could be used as a phosphorescent chemosensor for Hg2 + and acetonitrile (ACN). Upon addition of aqueous Hg2 +, the ACN solution of Ir1 gave a visual color change and significant phosphorescent enhancing (130-fold) at 580 nm (OFF–ON). Ir1 has been developed as an AND logic gate with Hg2 + and ACN as inputs.Display Omitted
Keywords: Cyclometalated iridium(III) complex; Phenylcinnoline; Chemosensor; Mercury(II); Logic gate; Acetonitrile;

An eight connected 3D porous coordination polymer, {[Cd(BTC)0.66(BPz)2] · 6H2O}n (1) (BTC = benzene-1,3,5-tricarboxylic acid, BPz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole) has been synthesized from hydrothermal reaction of Cd(NO3)2  · 4H2O with BPz and BTC. Complex 1 is a thermally stable microporous MOF having cubo-octahedral and octahedral cages as the Supermolecular Building Block (SBB) with an eight connected reo topology. It shows moderate N2 sorption (101 cm3 g− 1) at 77 K with a BET surface area of 330 m2 g− 1. Complex 1 also exhibits photoluminescent property in solid state with λ max at 397 nm.A novel eight connected porous metal-organic framework was synthesized and characterized by single crystal XRD. The cubo-octahedra (diameter 6 Å) and octahedral (diameter 3 Å) constitute the porous cages in the crystal. The gas sorption and solid state emission properties of the compound were studied.Display Omitted
Keywords: Hydrothermal; Cadmium(II); Metal-organic framework; Sorption; Luminescence;

A six connected 3D porous coordination polymer {[Cd(HBTC)(BPz)]·3EtOH}n (1) (H3BTC = benzene-1,3,5-tricarboxylic acid, BPz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole) has been synthesized from mild solvothermal reaction of Cd(NO3)2·4H2O with BPz and H3BTC in ethanol. Complex 1 is a thermally stable microporous MOF having (Cd2(COO)2) as the secondary building unit (SBU) with a six connected pcu topology. The pores of the polymer are decorated with free COOH groups which show moderate N2 sorption (38 cc g− 1) at 77 K with a BET surface area of 129 m2  g− 1. Complex 1 also exhibited photoluminescent property in solid state with λ max at 396 nm.A novel six connected porous metal–organic framework was synthesized and characterized by single crystal XRD. The compound has free carboxylic acid groups inside the pores due to which channels are subdivided into zones which are filled up with solvent molecules. The gas sorption and solid state emission properties were studied.Display Omitted
Keywords: Solvothermal; Cadmium (II); Metal–organic framework; Sorption; Luminescence;

Ruthenium(II) supported by phosphine-functionalized N-heterocyclic carbene ligands as catalysts for the transfer hydrogenation of ketones by Matthew E. Humphries; Wiktoria H. Pecak; Sallie A. Hohenboken; Samuel R. Alvarado; Dale C. Swenson; Gregory J. Domski (138-143).
We have prepared and characterized two ruthenium(II) complexes supported by phosphine-functionalized N-heterocyclic (NHC) ligands. One of the complexes (2a) underwent ortho-metalation of the N-phenyl moiety giving rise to a tridentate PCNHCC coordinating ligand whereas 2b bears an N-mesityl group in order to prevent C–H activation of the aryl ring thereby enforcing a PCNHC bidentate binding mode. Both 2a and 2b were shown to catalyze transfer hydrogenation of ketones at 82 °C in 2-propanol in the presence of KO t Bu albeit with vastly different catalytic activities. Catalytic transfer hydrogenation by 2b was shown to proceed at room temperature and in air using unpurified 2-propanol as solvent and hydrogen donor. Time studies revealed unique kinetic profiles for the two precatalysts; this may shed light on the difference in their catalytic activities.Two ruthenium(II) complexes supported by phosphine-functionalized N-heterocyclic carbene ligands have been prepared, characterized and evaluated as catalysts for transfer hydrogenation of ketones.Display Omitted
Keywords: N-heterocyclic carbene; Transfer hydrogenation; Ruthenium(II) complexes; Ortho-metalation;

Discrete trigonal prism nickel clusters: Syntheses, crystal structures and characterizations by Chunhong Tan; Zhenzhen Xue; Xiao Ma; Yanlong Wang; Yong Wang; Shenming Hu; Tianlu Sheng; Xintao Wu (144-147).
Two new nickel clusters, namely Ni6(μ-DTT)3 (DTT = dithiothreitol for 1, L-dithiothreitol for 1L), have been successfully synthesized and characterized. 1L is a chiral cluster. Single X-ray diffraction analysis reveals that clusters 1 and 1L are the first nickel thiolate clusters exhibiting a unique trigonal prismatic Ni6 structure.Two new nickel clusters which are the first nickel thiolate clusters exhibiting a unique trigonal prismatic Ni6 structure have been investigated and 1L is a chiral cluster.Display Omitted
Keywords: Nickel cluster; Trigonal prism; Thiolate ligand; Chiral;

Elemental sulfur has been applied as soft oxidant for facile one-pot preparation of air sensitive organometallic di[5]trovacenyldichalcogenides. This methodology successfully overcomes the dilemma between air instability and the required oxidation of corresponding substrates REH or RELi (E = S, Se, Te), and also avoids the usage of unstable chlorides E2Cl2 and transition metal catalysts. The oxidation ability of various oxidizing agents including free oxygen, elemental sulfur, selenium, tellurium, hydrogen peroxide and halogen has been investigated based on their electrochemical potentials. This study provides one convenient opportunity to prepare air sensitive organometallic dichalcogenide under mild reaction condition.Display Omitted
Keywords: Oxidation ability; Elemental sulfur; Air sensitive; Organometallic dichalcogenides;

Two new heteroleptic complexes, [Ni(Fcdpm)(Fcdtc)] 1 and [Pd(Fcdpm)(Fcdtc)] 2 (Fcdpm = 5-Ferrocenyl dipyrromethene, Fcdtc = N-benzyl-N-ferrocenylmethyl dithiocarbamate) have been prepared by the reaction of precursor homoleptic complexes [M(Fcdtc)2] (M = Ni(II), Pd(II)) and the ligand Fcdpm and characterized by elemental analysis, IR, 1H and 13C NMR and UV–vis. spectroscopy. Their structures have been elucidated by X-ray crystallography. In both complexes, 1 and 2 the central metal lies at the center of a distorted square plane chelated by nitrogen atoms of the Fcdpm and sulfur atoms of the Fcdtc ligands. In both complexes the structures are stabilized via C―H···S and CH···π secondary interactions resulting in 1D supramolecular motifs. The palladium complex 2 shows luminescent emission in solution.Luminescent [Ni/Pd(Fcdpm)(Fcdtc)] complexes.Display Omitted
Keywords: Dithiocarbamate; Dipyrromethene; Crystal structure; Fluorescence;

A new compound, namely [Zn2(pbdc)1.5(TAZ)]n 2nH2O (1 H2pbdc = terephthalic acid, HTAZ = 1H-1,2,4-triazole), has been hydrothermally synthesized from H2pbdc, HTAZ and Cd(II) salts. Single crystal X-ray diffraction analysis reveals that compound 1 represents an unprecedented (4,8)-connected 3D topological network. Notably, two TAZ ligands in uniform μ3-1,2,4 bridging mode connect four Zn(II) ions together, giving rise to a [Zn4(TAZ)2] metallo-ligand subunit, which are further bridged via pbdc ligands in two kinds of coordination modes, resulting in the final 3D complicated framework. The relevant density of states (DOS) calculation result showed that the luminescence of 1 mainly originates from HTAZ intraligand charge transition.Presented here is a new luminescent Zn(II) coordination polymer, namely [Zn2(pbdc)1.5(TAZ)]n (1 H2pbdc = terephthalic acid, HTAZ = 1H-1,2,4-triazole), which represents an unprecedented (4,8)-connected topological network.Display Omitted
Keywords: Zn(II); Hydrothermal reaction; Metallo-ligand; Luminescence;

A behavioural difference between an iron(II) grafted polyphosphazene and its small molecule cyclophosphazene analogue by Ross J. Davidson; Eric W. Ainscough; Andrew M. Brodie; Mark R. Waterland; Harry R. Allcock; Mark D. Hindenlang; Boujemaa Moubaraki; Keith S. Murray; Keith C. Gordon; Raphael Horvath; Guy N.L. Jameson (158-161).
Mössbauer and electronic absorbance spectroscopy along with variable temperature magnetic moment measurements demonstrate that a cyclotriphosphazene substituted with an iron(II)-bis-2,6-di(1H-pyrazoly-yl)pyridine moiety (1) and its polyphosphazene analogue (2) differ significantly in magnetic behaviour.A cyclotriphosphazene substituted with an iron(II)-bis-2,6-di(1H-pyrazoly-yl)pyridine moiety and its polyphosphazene analogue differ significantly in magnetic behaviour.Display Omitted
Keywords: Polyphosphazene; Iron(II); Spin-crossover;

A new compound, namely [Zn1.5(pbdc)(ATAZ)(OH)]n (1 H2pbdc = terephthalic acid, HATAZ = 3-amino-1,2,4-triazole), has been obtained by in situ aminotriazole ligand synthesis and characterized by elemental analysis, thermal analysis, as well as single crystal and powder X-ray diffraction analysis. Compound 1 exhibits a 3D pillar–layer framework based on Zn(II)-aminotriazole layers and pbdc pillars, which can be simplified into a 2-fold interpenetrated pcu topological network. Interestingly, two ATAZ ligands and two OH ligands bridge three Zn(II) ions together, giving rise to a new trinuclear {Zn3(ATAZ)2(OH)2} subunit. In addition, the luminescent and thermal stability properties for the title compound have also been studied.Presented here is a new luminescent Zn(II) coordination polymer, namely [Zn3(pbdc)(ATAZ)(OH)2]n (1 H2pbdc = terephthalic acid, HATAZ = 3-amino-1,2,4-triazole), which was constructed from H2pbdc and in situ generated HATAZ ligands.Display Omitted
Keywords: Zn(II) compound; In situ reaction; Pillar–layer framework; Luminescence;

Used versatile multidentate benzene-based bis-triazole ligand 1,3-di-(1,2,4-triazole-4-yl)benzene (L), two novel 3D porous Copper(II) and Zinc(II) frameworks, namely {[Cu(μ2-L)2(SiF6)(H2O)]·0.5H2O}n (1) and {[Zn33-L)6](NO3)6}n (2), have been isolated under the hydrothermal conditions. The structural analysis reveals that 1 presents a 3D microporous Copper(II) framework with the novel 4-connected 6383 dmp topology containing infinite right- and left-handed Cu(μ2-L)2 helical chains. While 2 presents a 3D cluster-based nano-porous cationic host framework with 6-connected α-Po-related (41263) topology, in which trinuclear Zinc(II) clusters can be defined as basic nodes. The varied temperature magnetic susceptibility of 1 (from 300 to 2 K) and solid state luminescent property of 2 also have been investigated.Two novel 3D porous frameworks with 1,3-di-(1,2,4-triazole-4-yl)benzene have been isolated. 1 presents a 3D microporous Cu(II) framework with 4-connected 6383 dmp topology, while 2 presents a 3D cluster-based nano-porous framework with 6-connected α-Po-related topology.Display Omitted
Keywords: dmp network; Trinuclear Zinc(II) clusters; Magnetic; Luminescent;

Herein we report a new strategy to synthesize zeolitic imidazolate framework-8 (ZIF-8) at a relatively low molar ratio of ligand to metal ion in aqueous solution under microwave irradiation for the first time. The products possess high surface area and large micropore volume. The molar ratio of ligand to metal ion and the salt anion play an important role on the size and shape of ZIF-8.Zeolitic imidazolate framework-8 (ZIF-8) was successfully synthesized by a new microwave irradiation method in aqueous solution for the first time.Display Omitted
Keywords: Rapid synthesis; Zeolitic imidazolate framework-8; Microwave; Aqueous;

Two new inorganic–organic hybrid compounds based on well-defined Keggin-type polyoxometalates and copper–bis(triazole) assemblies, namely, [Cu3(L)3(PMo12O40)2] · 9H2O (1) and [Cu3(L)3(PW12O40)2] · 9H2O (2) [L = 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene], have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR, and TG. To the best of our knowledge, compounds 1 and 2 represent rare 2D structural examples with POM clusters as pendants. In addition, the diffuse reflectivity spectra of these two compounds show that they can be regarded as a wide gap semiconductor. The photocatalytic experiments indicate that both 1 and 2 exhibit high catalytic activity for photodegradation of Rhodamine B (RhB) with UV irradiation.Two layered copper–bis(triazole) assemblies with Keggin polyoxoanions as pendants are presented that exhibit high catalytic activity for photodegradation of rhodamine B with UV irradiation.Display Omitted
Keywords: Inorganic–organic hybrid material; Hydrothermal synthesis; Polyoxometalate; Photocatalytic property;

Under similar hydrothermal synthetic conditions used, a novel flexible ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetonitrile (PPAN), benzenedicarboxylate isomers (H2ip = isophthalate, H2tp = terephthalate) and Zinc(II) acetate, two novel mixed-ligand Zn(II) coordination polymers {Zn3(PPAA)2(μ 4-ip)2}n (1) and {Zn2(PPAA)2(μ-tp)}n (2) (PPAA  = 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetate) have been isolated, in 1-2 PPAN ligand is also hydrolyzed into a novel PPAA ligand. Complex 1 contains 1D double chains of {[Zn(PPAA)]+}n cation structural units, which are further extended by these tetra-dentate μ 4-ip2−  ligands forming a novel 2D three-layered framework with (4.82)2(43.62.8)2(43.83)2(48.66.8) topology. While complex 2 contains bi-nuclear [Zn2(PPAA)2]2 + structural units, which are extended by four tetra-dentate μ-tp2−  ligands to link eight neighboring di-nuclear [Zn2(PPAA)2]2 + units ultimately forming a 3D framework with a lim symbol of (4.102)2(42.104) topology. The flexible coordination modes of PPAA and benzenedicarboxylate isomers also reveal a great potential in the construction of these novel mixed-ligand luminescent frameworks with diverse structural motifs and unique functional properties.This work presents two Zn(II) coordination polymers based on a novel 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetate and different benzenedicarboxylate isomers (isophthalate, terephthalate), which exhibit distinct 2D layered and 3D network coordination arrays.Display Omitted
Keywords: PPAA; Coordination polymer; Network topology; Luminescent;

A trinuclear [Zn3(L)2(OAc)2] complex based on the asymmetrical bis-Schiff-base ligand H2L for ring-opening copolymerization of CHO and MA by Luqun Zhu; Dengfeng Liu; Liying Wu; Weixu Feng; Xingmei Zhang; Jing Wu; Daidi Fan; Xingqiang Lü; Rong Lu; Qi Shi (182-185).
Based on asymmetrical bis-Schiff-base ligand H2L from o-vanillin and the half-unit Schiff-base precursor HL synthesized from 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and o-phenylenediamine, a trinuclear [Zn3(L)2(OAc)2] (1) is obtained. In complex 1, the unsaturated five and four-coordinate coordination environment for the catalytic active centers (Zn2 + ions) permits the monomer insertion for the effective bulk or solution copolymerization of CHO (cyclohexene oxide) and MA (maleic anhydride) in the presence of co-catalyst of DMAP (4-(dimethylamino)pyridine), TPP (triphenylphosphine) or n-Bu4NBr. All the bulk copolymerizations afford poly(ester-co-ether)s, while some of the solution copolymerizations produce perfectly alternating polyester copolymers. Of the three co-catalysts, DMAP is found to be the most efficient, while an excess thereof is detrimental for chain growth of the copolymers.A new trinuclear complex [Zn3(L)2(OAc)2] (1) based on the asymmetrical bis-Schiff-base ligand H2L, which is synthesized by the reaction of o-vanillin and the half-unit Schiff-base precursor HL from 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and o-phenylenediamine, is obtained and used for the effective bulk or solution ring-opening copolymerization of CHO (cyclohexene oxide) and MA (maleic anhydride).Display Omitted
Keywords: Trinuclear Zn2 + complex; Asymmetrical bis-Schiff-base ligand; Ring-opening copolymerization from CHO and MA; Polyester and poly(ester-co-ether);

Reinvestigation of the first structurally characterized metal-coordinated sulfenic acid complex by Rajat Chauhan; Mark S. Mashuta; Craig A. Grapperhaus (186-188).
Single crystal X-ray diffraction studies reveal a new crystal morphology of [Ru(DPPBT)(DPPBT-O2)(DPPBT-OH)] (DPPBT = 2-(diphenylphosphine)benzenethiolate; DPPBT-O2  = 2-(diphenylphosphine)benzene-sulfinate; DPPBT-OH = 2-(diphenylphosphine)benzenesulfenic acid) in the monoclinic space group C2/c. The sulfenic acid hydrogen, which was only inferred in the previously reported P-1 structure, has been located and refined. Comparison of metric data from the C2/c structure with density functional theory optimized structures (B3LYP/LANL2DZ + 6–31g(d)) definitively confirms the assignment of the complex as the Ru(II) sulfenic acid.The sulfenic acid proton of the only structurally characterized metal-coordinated sulfenic acid complex has been located and refined through a reinvestigation of the X-ray crystal structure of [Ru(DPPBT)(DPPBT-O2)(DPPBT-OH)].Display Omitted
Keywords: Sulfenic acid; Metal-coordination; Sulfinate; Sulfenate; X-ray crystallography; Density functional theory;

Facile fabrication of ruthenium(IV) oxide nanostructures by thermal decomposition of two new organoruthenium(II) complexes by Mao-Lin Hu; Vahid Safarifard; Ali Morsali; Tong-Le Shao; Xian-Chuan Li (189-192).
Two new monofunctional ruthenium(II) arene complexes of the type [(η 6-arene)Ru(ethylenediamine)(X)] n+ where arene is substituted benzene (p-cymene), and X are halide (Br and Cl), [(η 6-p-cymene)Ru(en)Br]Br (1) and [(η 6-p-cymene)Ru(en)Cl]PF6 (2), have been investigated. The X-ray crystal structures of both organoruthenium(II) complexes are reported. Both two complexes have “piano stool” geometries with η 6 coordination of the arene ligand. RuO2 nanoparticles were simply synthesized by solid-state transformation of compounds 1 and 2 at 400 °C under air atmosphere. The results show that the size and morphology of the RuO2 nanoparticles are dependent upon the starting organometallic ruthenium(II) complexes.Two new ruthenium(II) arene complexes of the type [(η 6-arene)Ru(ethylenediamine)(X)] n+ where arene is substituted benzene (p-cymene), and X are halide (Br and Cl), [(η 6-p-cymene)Ru(en)Br]Br (1) and [(η 6-p-cymene)Ru(en)Cl]PF6 (2), have been investigated. The X-ray crystal structures of both organoruthenium(II) complexes are reported. RuO2 nanoparticles were simply synthesized by solid-state transformation of compounds 1 and 2 at 400 °C under air atmosphere.Display Omitted
Keywords: Organoruthenium(II); Nanostructure; Thermal decomposition; Ruthenium(IV) oxide;

Mixed valence cobalt (II, III) systems, one binuclear CoIIICoII (1) and another novel cyclic trinuclear CoIIICoII 2 (2) complexes based on hydroxyl rich Schiff base ligands are synthesized and structurally characterized by X-ray crystallography. Catalytic activity of 1 and 2 towards oxidation of 3, 5-di-tert-butylcatechol (3,5-DTBC) to its corresponding quinone (3,5-DTBQ) are investigated in MeOH and DMF. ESI-MS technique is employed to characterize the intermediates.Display OmittedNew dinuclear and cyclic trinuclear mixed valance complexes are developed that exhibit efficient catecholase activity. The second complex is the first structurally characterized cyclic trinuclear mixed valance cobalt complex without μ-3 bridging showing catecholase activity.
Keywords: Cobalt (II, III); Crystal structures; Catecholase activity;

Structures, luminescence and magnetic properties of three 3D lanthanide–zinc heterometallic coordination polymers based on 3-amino-1,2,4-triazole and Oxalate by Jin-Ying Gao; Ning Wang; Xia-Hua Xiong; Chu-Jun Chen; Wei-Ping Xie; Xing-Rui Ran; Yi Long; Shan-Tang Yue; Ying-Liang Liu; Yue-Peng Cai (197-201).
Three 3D Ln(III)–Zn(II) 3d-4f heterometallic coordination polymers (HCPs) constructed from the coligands 3-amino-1H-1,2,4-triazole and oxalate, {[Ln2Zn19(atz)18(ox)9(Cl)8]·17H2O}n(Ln = Eu 1, Gd 2, Tb 3, Hatz = 3-amino-1H-1,2,4-triazole, ox = oxalic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, FT-IR, TG analysis and X-ray diffraction. X-ray diffraction analysis reveals that these complexes are isostructural and feature 3D pillar-layered coordination frameworks constructed by the linkages of 2D layers and 1D zigzag chains, possessing a 5-nodal net topology with Schläfli symbol of {32;52;62}3{33;44;57;65;72}6{33;45;55;6;7}6{36;415;56;6}2{53}4. In addition, the magnetic property of 2 and the luminescence properties of 1 and 3 were also investigated.The neighboring 2D planars connected together into a 3D supramolecular architecture by Hatz ligand. All amino groups were omitted for clarity.Display Omitted
Keywords: Hydrothermal synthesis; Lanthanide ion; Topology; Luminescence;

A heptanuclear heterotrimetallic [Na2Cr2Tb3] cluster exhibiting single-molecule magnet behavior by Hui Zhang; Zhong-Yi Li; Jiang Zhu; Yong-Xian Yu; Jun Ni; Bao-Jun Ding; De-Zhi Liu; Jian-Jun Zhang (202-205).
With maleic acid as the ligand, a heterotrimetallic cluster {[Na(H2O)][Na2Cr2Tb33-OH)6(L)6(H2O)17]}⋅16H2O (H2L = maleic acid) (1) bearing a bicapped trigonal bipyramidal [Na2Cr2Tb3] metal skeleton was synthesized and characterized. Magnetic measurements indicate that 1 displays overall ferromagnetic interactions and slow relaxation of the magnetization.The synthesis and characterization of a new maleate-based bicapped trigonal bipyramidal [Na2Cr2Tb3] cluster exhibiting overall ferromagnetic interaction and slow relaxation of the magnetization are presented.Display Omitted
Keywords: Heptanuclear; Heterotrimetallic; Maleic acid; Bicapped trigonal bipyramid; Slow relaxation of the magnetization;

Polycatenation and photoluminescence of two zinc coordination polymers based on arched and linear mixed ligands by Jin-Shuang Guo; Ming-Jian Zhang; Cui-Juan Zhang; Xiao-Ming Jiang; Guo-Cong Guo; Jin-Shun Huang (206-210).
Two polycatenated coordination polymers, {[Zn3(adc)3(bpp)4]2  · 3H2O} n (1) and [Zn(adc)(bphy)] n (2) (adc = azobenzene-4,4′- dicarboxylate, bpp = 1,3-bis(4-pyridyl)propane, bphy = 1,2-bis(4-pyridyl)hydrazine), have been obtained from Zn(NO3)2∙ 6H2O, linear H2adc ligand and arched bpp/azpy (azpy = 4,4′-azobispyridine) ligands by hydro(solvo)thermal reactions. Compound 1 presents a 2-D structure catenated from 1-D double ladders (1-D → 2-D polycatenation), while compound 2 displays a 3-D structure catenated from 2-D (4,4) stair-stepping layers (2-D → 3-D polycatenation). Luminescence properties of 1 and 2 have been explored, together with study of photoluminescent mechanism by density of states (DOS) calculation.Two new coordination polymers presenting polycatenations and photoluminescence properties have been obtained through a mixed-ligand strategy using arched and linear ligands.Display Omitted
Keywords: Arched ligand; Coordination polymer; Photoluminescence; Polycatenation;

Synthesis and structure of a novel gallium diphosphonate by Xiaomin Hou; Lingling Tan (211-213).
One new gallium diphosphonate, Ga[(HPO3)(H0.5PO3)CHNH2Py]2 (1), has been hydrothermally synthesized and characterized by elemental analysis, IR, EDS, TGA–DSC, UV–vis, powder and single-crystal X-ray diffraction methods. Its structure contains Ga-centered octahedra which are linked together by the two ―PO3 groups of the diphosphonate ligands to form one-dimensional infinite chain along a-axis. TGA–DSC measurement indicates that this compound is thermally robust.The reaction of one diphosphonate ligand, N-(2-Pyridyl)-aminomethane-1,1-diphosphonic acid, with gallium nitrate afforded one gallium diphosphonate, Ga[(HPO3)(H0.5PO3)CHNH2Py]2. It was fully characterized by EA, EDS, IR, UV/vis, TGA-DSC, powder and single-crystal X-ray diffraction methods. It has a one-dimensional infinite chain structure which are assembled from Ga-centered octahedra and linking diphosphonate ligands.Display Omitted
Keywords: Metal phosphonates; Synthesis; Structure; Gallium; Stability;

Two new porous metal-organic frameworks based on the versatile terephthalate ligands and well-known Mn3 SBUs, namely [Mn1.5(tpa)1.5(MeOH)2]·(MeOH) (1) and [Mn1.5(tpa)(Htpa)]·(Solvent)x (2), have been prepared through altering solvent system. Single-crystal X-ray analysis reveals that their porosity is mainly dependent on the coordination ability of solvent molecules. Their structures are closely correlated with that of other two reported compounds ([Mn1.5(tpa)1.5(DMA)2(3) and [Mn1.5(atpa)(Hatpa)]·(4), DMA = N,N′-dimethylacetamide and H2atpa = 2-aminoterephthalic acid). Topological analysis is used to improve our understanding for the general feasibility to tune their porosity. The distinct porosity of two compounds has also been characterized by N2 adsorptions. Compound 2 has a type I adsorption isotherm with an appreciable adsorption of 74.72 cm3g− 1 at 0.35 P/P0, whereas 1 exhibits a maximum uptake of 19.84 cm3g− 1 at approximately 1 atm.Herein, two new porous metal-organic frameworks based on the versatile terephthalate ligands and well-known Mn3 SBUs, namely [Mn1.5(tpa)1.5(MeOH)2]·(MeOH) (1) and [Mn1.5(tpa)(Htpa)]·B(Solvent)x (2), have been prepared through altering solvent system. Single-crystal X-ray analysis reveals that their porosity is mainly dependent on the coordination ability of solvent molecules. The distinct porosity of two compounds has also been characterized by N2 adsorptions. Compound 2 has a type I adsorption isotherm with an appreciable adsorption of 74.72 cm33Pg− 1 at 0.35 P/P0, whereas 1 exhibits a maximum uptake of 19.84 cm33Pg− 1 at approximately 1 atm.Display Omitted
Keywords: Mn3-frameworks; Terephthalic acid; Porosity; Solvent system; N2 adsorptions;

Synthesis and crystal structures of uranium (VI) and thorium (IV) complexes with picolinamide and malonamide by Yingjie Zhang; Mohan Bhadbhade; Jiabin Gao; Inna Karatchevtseva; Jason R. Price; Gregory R. Lumpkin (219-221).
Calixarene-based picolinamides and malonamides are among the promising extracting ligands for selective separation of minor actinides. However, the understanding of coordination chemistry of actinide ions with simple picolinamide- and malonamide-type ligands is still far from comprehensive. In this work, we report the first two picolinamide coordinated uranium (VI) and thorium (IV) complexes with different 1D polymeric structures as well as a malonamide coordinated uranium (VI) molybdate with a 2D layered structure.The understanding of coordination chemistry of actinide ions with simple picolinamide- and malonamide-type ligands is important in better design of extracting ligands for selective separation of minor actinides. In this paper, we report the synthesis and characterisation of the first two picolinamide coordinated uranium (VI) and thorium (IV) complexes with different 1D polymeric structures and a malonamide coordinated uranium (VI) molybdate with a 2D layered structure.Display Omitted
Keywords: Uranium; Thorium; Minor actinides; Picolinamide; Malonamide;

Structurally characterized zwitterionic chiral zinc imidazolium [4,4] grid by Chatla Naga Babu; Arruri Sathyanarayana; Shaikh M. Mobin; Ganesan Prabusankar (222-224).
The first zwitterionic chiral imidazolium carboxylate supported molecular [4,4] grid lamellae have been synthesized and characterized.The first zwitterionic chiral imidazolium carboxylate supported molecular [4,4] grid lamellae have been synthesized and characterized.Display Omitted
Keywords: Zinc; Imidazolium carboxylate; Chiral; Coordination polymer;

Easy access to the Wilkinson tris(tert-butylimido)nitridomanganate(VII) complex from commercially available starting materials by Jeffrey D. McCall; Shivaiah Vaddypally; Sandeep K. Kondaveeti; Michael J. Zdilla (225-227).
The synthesis of dark green, crystalline Li2[Mn(N t Bu)3  N] ∙ LiCl(THF)2 in two steps from commercially available starting materials is described. Reaction of MnF3 with LiNH t Bu and LiCl and subsequent workup represents an easy access to this historic complex. 1H NMR, absorption and FT-IR spectra, and single crystal X-ray diffraction data are reported and confirm the identity of the material.The tris(terminalimido)nitridomanganate(VII) of Danopoulos and Wilkinson is finally available via a simple, two-step synthesis from commercially available, inexpensive starting materials.Display Omitted
Keywords: Manganese; Imide; Nitride;