Inorganic Chemistry Communications (v.40, #C)

Contents List (iii-xvi).

Catalytic enantioselective Friedel–Crafts alkylations of indoles and nitroalkenes were carried out by using a new heterotrimetallic Cu/Eu/Cu complex catalyst based on the simple chiral ligand, reduced Schiff base 1, to give the Friedel–Crafts adducts with up to 88% yield and 80% ee. The trimetallic catalyst is air-stable and can be formed in-situ by a facile solution self-assembly during the catalytic reaction.Catalytic enantioselective Friedel–Crafts alkylations of indoles and nitroalkenes were carried out by using a new heterotrimetallic Cu/Eu/Cu complex as catalyst based on the simple chiral ligand, reduced Schiff base, affording the Friedel–Crafts adducts with up to 88% yield and 80% ee.Display Omitted
Keywords: Friedel–Crafts alkylation; Asymmetric catalysis; Salan ligand; Heterotrimetallic complex;

Influence of Sm3 + doping on the dielectric properties of CaCu3Ti4O12 ceramics synthesized via autocombustion by Alex Lopera; Miguel Angel Ramirez; Claudia García; Carlos Paucar; Jairo Marín (5-7).
Ca1 − xSmxCu3Ti4O12 (x = 0.0, 0.2, 0.3) electronic ceramics were fabricated via the chemical route using metal nitrate solutions in order to improve the dielectric properties of this ceramic. X-ray diffraction (XRD) analysis indicated the formation of a single CaCu3Ti4O12 (CCTO). Grain size of the samples doped with Sm3 + was in the range of 1–2 μm, as opposed to 50–100 μm in the pure samples of CCTO. The cutoff frequency with the doping was remarkably shifted, from 1 MHz (pure CCTO) to 10 MHz (doped CCTO). Meanwhile, the real dielectric (εr) and imaginary dielectric (ε″) constants showed a decrease as the doping was increased.Powders of calcium copper titanate (CCTO) doped with Sm3 + were synthesized by autocombustion technique.X-ray diffraction (XRD) showed that autocombustion technique produces the main phase of CCTO.Scanning electron microscopy (SEM) showed the decrease of the grain size of CCTO.Impedance spectroscopy (IS) showed that doping with Sm3 + shifted the CCTO cutoff frequency.Display Omitted
Keywords: CCTO; Samarium; Citrate–nitrate route; Dielectric properties;

Solvothermal synthesis and structural characterization of a Cd-triazole-benzenedicarboxylate framework by Wen-E Li; Fu-Hong Liu; Xiao-Ming Liu; Kun Zhou; Liang Zhao; Xiao-Li Hu; Zhong-Min Su (8-10).
By employing mixed-ligands of 1,4-H2BDC and Htrz (1,4-H2BDC = 1,4-dicarboxybenzene, Htrz = 1-H-1,2,4-triazole) under solvothermal condition, a metal-organic framework, [(CH3)2NH2][Cd2Cl(1,4-BDC)(Trz)2] (1), has been synthesized and characterized by single crystal X-ray diffraction. Compound 1 exhibits a three-dimensional structure with two kinds of channels along the c axis. In addition, powder X-ray diffraction, thermogravimetric analysis and photoluminescent properties of 1 were investigated in detail.A Cd-triazole-benzenedicarboxylate framework has been synthesized under solvothermal condition exhibiting a three-dimensional structure with two kinds of channels along the c axis.Display Omitted
Keywords: Metal–organic framework; 1-H-1,2,4-triazole; Solvothermal; Photoluminescent;

We describe herein the synthesis of supramolecular metallocyclodextrins containing multiruthenium centers. These compounds exhibit especially strong fluorescence and electrochemiluminescence (ECL), as well as excellent quenching efficiency because of their ability to perform host–guest recognition.Multiruthenium metallocyclodextrins Ru-CD, 2Ru-CD and 3Ru-CD were successfully synthesized. 3Ru-CD exhibited an excellent fluorescence and electrochemiluminescence (ECL) characteristic among the three complexes. Our research demonstrated that 3Ru-CD will be a new ECL luminophore, and it will have a great potential in the field of photo-electronic devices and ECL.Display Omitted
Keywords: Cyclodextrins; Metallocyclodextrin; Host–guest recognition; Binding;

The first zeolitic pure germanate built up from the four-membered ring — CCUT-9 showing high surface area by Ya-feng Li; Wen-yuan Gao; Xiao-lin Qin; Jing-jing Lu; Yan Liu (15-17).
CCUT-9, the first zeolitic pure germanate built up from the four membered ring, has been hydrothermally synthesized by the co-templated method of alkali and organic amine. The structural determination gives rise to the neutral framework of CCUT-9 with solvent free void of 1085 Å3 (17.39%). Furthermore, the N2 isothermal adsorption shows that CCUT-9 possesses a Langmuir surface area of 586 m2/g (lower P/P0), corresponding to a BET surface area of 811 m2/g (higher P/P0).CCUT-9, a zeolitic pure germanate built up from the four-membered ring, displays the high surface area (Langmuir surface area of 586 m2/g and BET surface area of 811 m2/g).Display Omitted
Keywords: Hydrothermal method; Germanate; Zeolite;

Amine- and sulfide-sensing copper(I) iodide films by James P. Killarney; Meaghan McKinnon; Caitlin Murphy; Kylie M. Henline; Charles Wang; Robert D. Pike; Howard H. Patterson (18-21).
Copper(I) iodide films were cast onto glass from solution. The CuI films absorb vapor-phase amine and sulfide molecules, producing a range of photoluminescent emission colors. Spectroscopic data suggest the presence of low energy CuI cluster-centered transitions.Copper(I) iodide films cast on glass absorb vapor-phase amine and sulfide molecules, producing a range of photoluminescent emission colors. Spectroscopic data suggest the presence of low energy CuI cluster-centered transitions.Display Omitted
Keywords: Copper iodide; Luminescence; Sensing; Volatile organic compounds; Films; Photophysics;

Synthesis, structure, and photocatalytic hydrogen of three environmentally friendly titanium oxo-clusters by Yin Lin; Yan-Fei Zhu; Zhi-Hui Chen; Fu-Hong Liu; Liang Zhao; Zhong-Min Su (22-25).
In this paper, three environmentally friendly titanium oxo-clusters, Ti6O4(OEt)4(OPri)4(OOCC6H5)8 (1), Ti6O4(OEt)8[OOC(CH3)3]8 (2) and Ti6O4(OCH3)8[OOC(CH3)3]8 (3), were obtained under three similar solvent-thermal reactions of titanium(IV) isopropoxide, alcohols and carboxylic acids, and structurally characterized by single-crystal X-ray diffraction, TGA and IR analysis. All the compounds were crystallized in the space group P21/c and the arrangements of the titanium atoms are similar. In addition, the UV-light photocatalytic hydrogen evolution activities have been observed for them, which showed good photocatalytic activity for hydrogen production from water.Three titanium oxo-clusters containing {Ti6O4} core are presented that exhibit photocatalytic hydrogen activities for hydrogen production from water splitting under UV irradiation.Display Omitted
Keywords: Titanium cluster; Metal alkoxide; Photocatalytic hydrogen;

A new cyano-bridged bimetallic complex [Mn(5-Clsaltmen) (H2O)(CH3OH)]{[Mn(5-Clsaltmen)(H2O)] W(CN)8[Mn(5-Clsaltmen)(CH3OH)]}·3.5H2O·2CH3OH [5-Clsaltmen =  N,N′-(1,1,2,2-tetramethylethylene) bis(5-chlorosalicylideneiminato) dianion] (1) was synthesized and structurally characterized by X-ray single-crystal diffraction. The structure of 1 consists of the asymmetric V-shaped Mn–W–Mn trinuclear anions, in which W(V) coordinates with [Mn(5-Clsaltmen)(H2O)]+ and [Mn(5-Clsaltmen)(CH3OH)]+ through the neighboring cyano bridges, isolated cations [Mn(5-Clsaltmen) (H2O)(CH3OH)]+ and lattice water and methanol molecules. The magnetic studies for 1 reveal that antiferromagnetic interactions (J  = − 4.6 cm− 1) between WV and MnIII centers is operating within the trimer.A new cyano-bridged bimetallic complex [Mn(5-Clsaltmen)(H2O)(CH3OH)] {[Mn(5-Clsaltmen)(H2O)]W(CN)8[Mn(5-Clsaltmen)(CH3OH)]}·3.5H2O·2CH3OH [5-Clsaltmen =  N,N′-(1,1,2,2-tetramethylethylene)bis(5-chlorosalicylideneiminato) dianion] (1) was synthesized and structurally characterized by X-ray single-crystal diffraction. Magnetic studies for 1 reveal that antiferromagnetic interactions (J  = − 4.6 cm− 1) between WV and MnIII centers are operating within the cyanide-bridged WMn2 trimer.Display Omitted
Keywords: Octacyanotungstate(V); Manganese(III) Schiff-base; Magnetic properties; Crystal structure;

Nonporous homochiral copper-based coordination polymers for enantioselective recognition and electrocatalysis by Guangju Zhang; Fangfang Zhao; Hailiang Hu; Hao Li; Huan Dong; Xiao Han; Hui Huang (31-34).
A pair of nonporous enantiomers [Cu(H2O)(bpy)(l-DBTA)]·H2O (L-1) and [Cu(H2O)(bpy)(D-DBTA)]·H2O (D-1) (l-DBTA = (-)-dibenzoyl-l-tartaric acid, d-DBTA = (+)-dibenzoyl-d-tartaric acid, bpy = 4,4′-bipyridine) with interdigitated architecture possess excellent enantioselective recognition and electrocatalysis ability towards l- and/or d-tart.Copper-based chiral nonporous enantiomers with interdigitated architecture possess excellent enantioselective recognition and electrocatalysis ability.Display Omitted
Keywords: Nonporous; Homochiral coordination polymers; Chiral catalysis; Enantioselective recognition;

Synthesis, crystal structure and catalytic property of a samarium complex with Hpytza [Hpytza = 5-(3-pyridyl) tetrazole-2-acetic acid] by Dian-Yu Chen; Jian-Hua Zou; Wu-Xiang Li; Bo Xu; Qiao-Yun Li; Gao-Wen Yang; Juan Wang; Ya-Mei Ding; Ying Zhang; Xiao-Feng Shen (35-38).
A reaction of SmCl3·6H2O and Hpytza (Hpytza = 5-(3-pyridyl) tetrazole-2-acetic acid) under the presence of KOH, produced a novel coordination compound, [Sm(pytza)2Cl(H2O)2] (1). This compound was structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compound 1 reveals an 1D structure via its bridging pytza ligand and simultaneously shows a specific and good catalytic behavior for the photo-polymerization of vinyl monomers. Furthermore, the high molecular weight polymers with narrow polydispersity were obtained, and the polymerization showed controlled characteristics. The catalyst can be isolated from polymer products easily and reused for at least 10 times.A novel 1D chain samarium(III) coordination polymer containing the pytza ligand was prepared. The samarium(III) compound showed a specific and good catalytic behavior for the photo-polymerization of vinyl monomers.Display Omitted
Keywords: Sm(III); Hpytza; Crystal structure; Catalytic polymerization;

Thiol-ionic liquid (SHIL) is prepared and used as bridge to prepare multi-component soft hybrids materials Ag(Ag2S)-SHIL-Ln(L)4 (Ln = Eu, Sm, L = TTA (thenoyltrifluoroacetylacetone), TAA (trifluoroacetylacetone), DBM (1,3-diphenyl-1,3-propanepione)) for its good solubility and functionality. Luminescence color of these soft hybrid materials can be adjusted through controlling different proportion of beta-diketonates (TTA, TAA, DBM) and silver species (Ag, Ag2S). Especially the white luminescence can be realized for the special composition of Ag/Ag2S and lanthanide beta-diketonate. The result can be expected to prepare luminescent soft materials to obtain the multi-color and white luminescence.Soft hybrids Ag(Ag2S)-SHIL-Ln(L)4 are assembled through an ionic liquid compound linkage. The white luminescence integration can be realized for special composition of hybrid systems.Display Omitted
Keywords: Photophysical property; Luminescence integration; Soft materials; Lanthanide complex; Silver component; Ionic liquid bridge;

A novel heterobimetallic coordination polymer, [Cd8Na(ntc)6(H2O)8] (1), (H3ntc = 5-nitrobenzene-1,2,3-tricarboxylic acid) has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. By topology analysis, the complicated architecture of 1 is simplified to be the 6-connected α-Po (pcu) net, which is built on the unprecedented heterobimetallic Cd2Na(CO2)6 MBB. Further, a 3D Cd/Na–O framework with diamond topology was obtained on condition that all the carbon atoms were neglected. In addition, the thermal stabilities and fluorescent properties were also studied.A novel Cd/Na coordination polymer which is built on the unprecedented heterobimetallic Cd2Na(CO2)6 MBB has been prepared. Compound 1 can be simplified as the 6-connected α-Po (pcu) net. A 3D Cd/Na–O framework with diamond topology was obtained on condition that all the carbon atoms were neglected.Display Omitted
Keywords: Heterobimetallic; 5-Nitro-1,2,3-benzenetricarboxylic acid; α-Po net; Fluorescent;

The one-pot reaction of (1S,2S)-(+)-1,2-diaminocyclohexane, 3-tert-butyl-2-hydroxybenzaldehyde and Zn(OAc)2·1.5H2O in methanol under reflux gives the diastereoselective formation of the first zinc(II)-salen double helicate, P-(S, S)-1, which adopts a right-handed helicity. The stereochemistry of the helicates can be readily tuned through varying the chiral diamine backbone.The one-pot diastereoselective formation of the first zinc(II)-salen double helicates is described, and the stereochemistry of the helicates can be readily tuned by altering the chiral diamine backbones.Display Omitted
Keywords: Zn(II); Salen ligand; Diastereoselective assembly; Helicate; Self-assembly;

A 3D Keggin-based framework containing AgI-ribbons and cycles by using rigid tetrazole-based ligand by Aixiang Tian; Xiaoling Lin; Na Sun; Jun Ying; Juwen Zhang; Na Li; Xiuli Wang (51-54).
A new Keggin-type polyoxometalate (POM)-based compound, [Ag9(ptz)5][PMoVI 11MoVO40]·H2O (1) (ptzH = 5-phenyl-1H-tetrazole), was synthesized under hydrothermal conditions. Compound 1 exhibits a 2D layer containing AgI ribbons and hexa-nuclear AgI circles, which are further linked by AgI atoms and [PMoVI 11MoVO40]4 − anions to construct a 3D framework. The electrochemical properties of compound 1 have been investigated.A new Keggin-based compound, [Ag9(ptz)5][PMoVI 11MoVO40]·H2O (1) (ptzH = 5-phenyl-1H-tetrazole), was synthesized under hydrothermal conditions. Compound 1 exhibits a 2D layer containing AgI ribbons and hexa-nuclear AgI circles, which are further linked by AgI atoms and [PMoVI 11MoVO40]4 − anions to construct a 3D framework. The electrochemical properties of compound 1 have been investigated.Display Omitted
Keywords: Keggin polyoxometalate; Hydrothermal synthesis; Rigid ptz ligand; Electrochemical property;

Bi6O5(OH)3(NO3)5·3H2O was successfully prepared by a very facile direct hydrolysis process. The as-prepared samples were characterized by XRD, SEM, DRS and PL. Bi6O5(OH)3(NO3)5·3H2O has an indirect-transition optical band-gap of 3.45 eV, and the ECB and EVB are estimated to be 0.75 eV and 4.20 eV, respectively. The as-prepared Bi6O5(OH)3(NO3)5·3H2O products showed different morphologies and microstructures with the change of pH value. The photocatalytic activities of the samples were determined by photooxidative decomposition of rhodamine-B (RhB) in aqueous solution. The results revealed that the sample obtained at pH 5 exhibited the highest photocatalytic activity, which is much better than P25 and Bi-based photocatalyst Bi2O2CO3.Bi-based photocatalyst Bi6O5(OH)3(NO3)5·3H2O was successfully developed. The pH value plays an important role in controlling the crystallization, morphology, and photocatalytic activity.Display Omitted
Keywords: Hydrolysis; Photocatalyst; Bi-based oxysalts; pH value;

Synthesis, crystal structure and water-induced reversible crystal-to-amorphous transformation property of [Co2(2,4-pydc)2(bpa)(H2O)6](H2O)2 by Jureepan Piromchom; Nanthawat Wannarit; Jaursup Boonmak; Chaveng Pakawatchai; Sujittra Youngme (59-61).
The dinuclear CoII coordination compound with empirical formula [Co2(2,4-pydc)2(bpa)(H2O)6](H2O)2 (1); bpa = 1,2-bis(2,4-pyridyl)ethane, 2,4-pydc = 2,4-pyridinedicarboxylate anion, has been synthesized and õcharacterized by elemental analysis, single crystal X-ray diffraction, IR and UV–vis spectra, TGA and XRPD. Compound 1 is a symmetry-related dinuclear compound consisting of two six coordinated cobalt atoms, one bpa ligand, two 2,4-pydc ligands and two lattice water molecules. Each CoII ion is coordinated by one oxygen atom and one nitrogen atom from 2,4-pydc bidentate chelate ligand, one nitrogen atom of bpa bidentate bridging ligand and three water molecules, giving a distorted octahedral geometry with CoN2O4 chromophore. The crystal packing of this compound reveals a novel 3D supramolecular network, formed by hydrogen-bonding and C–H⋯π interactions. Investigations of the dynamic structural transformation behavior demonstrate that the title compound exhibits a solvent-induced reversible crystal-to-amorphous transformation with chromotropism when exposed to water vapor. This indicates that the dehydrated amorphous form, Co2(2,4-pydc)2(bpa)(H2O)2 (1A), may be utilized as an indicator for humidity.The dinuclear CoII compound, [Co2(2,4-pydc)2(bpa)(H2O)6](H2O)2 (1); bpa = 1,2-bis(2,4-pyridyl)ethane, 2,4-pydc = 2,4-pyridinedicarboxylate anion has been synthesized and fully characterized. This compound exhibits a solvent-induced reversible crystal-to-amorphous transformation with chromotropism.Display Omitted
Keywords: Dinuclear cobalt(II); 2,4-Pyridinedicarboxylic acid; 1,2-Bis(4-pyridyl)ethane; Hydrogen bonding; Structural transformation;

Two luminescent metal − organic frameworks constructed by unsymmetric tricarboxylate by Xiao Chen; Ying Tong; Min-Min Han; Ke-Li Cao; Yun-Long Feng (62-65).
Two metal–organic frameworks, Zn(Hbpt)(bpp) (1), [Cd(Hbpt)(bpp)(H2O)] (2), (H3bpt = biphenyl-3,4′,5-tricarboxylate, bpp = 1,3-bi(4-pyridyl)propane), have been solvothermally synthesized from unsymmetric tricarboxylate and nitrogen containing ligands, and characterized by single-crystal and powder X-ray diffractions, FTIR, and TGA. Single-crystal X-ray structural analyses show that 1 possesses a 2D grid layer consisting of Zn ions bridged by bpp ligands and partly deprotonated Hbpt2 − ligands, which is extended via hydrogen bonds to a two-fold interpenetrated framework. 2 contains 1D ladder-like chains, which are further linked by hydrogen bonds into the 3D supramolecular architecture. Furthermore, photoluminescence studies revealed that these coordination polymers display intense violet emission in the solid state at room temperature.Two d10 metal − organic frameworks (MOFs) based on biphenyl-3,4′,5-tricarboxylate (H3bpt) and 1,3-bi(4-pyridyl)propane (bpp), Zn(Hbpt)(bpp) (1), [Cd(Hbpt)(bpp)(H2O)] (2), were obtained and characterized. 1 features a 2D grid layer and 2 affords a 1D ladder-like chain. The MOFs exhibit interesting fluorescent dual emission in the solid state.Display Omitted
Keywords: Metal–organic frameworks; Crystal structure; Unsymmetric carboxylate; Luminescence;

In this paper, two novel ligands (H3L1, H2L2) have been synthesized from diethylene triamine pentaacetic acid (DTPA) and isoniazid in different conditions. H3L1 has three carboxylic groups, and H2L2 has two carboxylic groups. Their non-ion complexes of GdL1 and MnL2 holding promise of magnetic resonance imaging (MRI) are synthesized, and relaxivity of complexes are determined, respectively. The relaxivity of GdL1 (R1  = 6.07 L·mmol−1·s−1) and MnL2 (R1  = 6.94 L·mmol−1·s−1) are larger than that of Gd(DTPA)2− (R1  = 4.34 L·mmol− 1·s−1). It is more significative that relaxivity of MnL2 is larger than that of GdL1. The results showed that two non-ion complexes are prospective MRI contrast agents.Two novel ligands have been synthesized from diethylene triamine pentaacetic acid and isoniazid in different conditions. Their non-ion complexes are synthesized, and relaxivity of complexes are determined. The relaxivity of complexes are larger than that of Gd(DTPA)2−. The results showed that two non-ion complexes are prospective MRI contrast agents.Display Omitted
Keywords: Non-ion complex; Relaxivity; MRI contrast agent;

Mononuclear sodium(I) and copper(I) silanethiolates by Sylwia Godlewska; Katarzyna Baranowska; Anna Dołęga (69-72).
Sterically encumbered ligand (ArO)3SiS, where Ar = 2,6-diisopropylphenyl, was employed for the synthesis of a dicoordinate copper(I) complex. The ligand creates a very hydrophobic environment around the metal center as indicated by the crystal structures and FT-IR spectroscopy.Sterically encumbered ligand (ArO)3SiS where Ar = 2,6-diisopropylphenyl was employed for the synthesis of a dicoordinate copper(I) complex. The ligand creates a very hydrophobic environment around the metal center as indicated by the crystal structures and FT-IR spectroscopy.Display Omitted
Keywords: Copper; Sodium; Silanethiolate; Crystal structure; Weak interactions;

Three mononuclear silver(I) complexes with 8-hydroxyquinoline, 8-hydroxy-2-methylquinoline and 5-chloro-8-quinolinol were synthesized and characterized by elemental analysis, NMR, ESI-MS as well as single crystal X-ray diffraction analysis. All the structures of complexes 13 with the silver center adopting an approximately four-coordinated distorted tetragonal pyramid geometry were found to exhibit selective cytotoxicity against HepG2, NCI-H460, BEL-7404 and HeLa cell lines with IC50 values generally in the micromolar range (1.7–14.6 μM), but low cytotoxicity towards normal human liver cell HL-7702. A combination of flow cytometric analysis and molecular probe observation indicated that complexes 13 could induce HepG2 cell apoptosis. Molecular mechanism studies suggested that complexes 13-induced apoptosis is mediated through the intrinsic apoptotic pathway with changes in mitochondrial membrane potential by finally activating effector caspase-3/9 to trigger cell apoptosis. Further studies revealed that complexes 1 and 2 caused cell cycle arrest at S phase, while complex 3 induced G1 cell cycle arrest in HepG2 cells. Taken together, these results suggest that complexes 13 may be potential candidates for cancer therapy.Three mononuclear silver(I) complexes were synthesized and checked the anti-cancer effect in four cancer cell lines. Our results suggested that complexes 1-3-induced apoptosis is mediated through the intrinsic apoptotic pathway with changes in mitochondrial membrane potential by finally activating effector caspase-3/9 to trigger cell apoptosis.Display Omitted
Keywords: Quinoline-based; Silver(I) complexes; Cytotoxicity; Cell cycle; Apoptosis; Anticancer activity;

N–O bidentate ligands, such as 8-quinolinol and aminoacids, in combination with the dinuclear precursor [{Rh(μ-OMe)(COD)}2] are versatile catalytic systems. Thus, stereoregular polymerization of phenylacetylene (PA) is observed in the presence of secondary amines. Interestingly, the outcome of the catalysis changes drastically on addition of strong coordinating phosphines, giving the product of the intermolecular anti-Markovnikov hydroamination of phenylacetylene.The combination of the dinuclear precursor [{Rh(μ-OMe)(COD)}2] with N–O bidentate ligands can be tuned to perform hydroamination or phenylacetylene polymerization.Display Omitted
Keywords: Rhodium; Hydroamination; Polymerization; Phenylacetylene; Aminoacid; 8-quinolinol;

Selective oxidation of sulfides to sulfoxides with urea hydrogen peroxide in the presence of the manganese complex of non-, partially and fully brominated meso-tetraphenylporphyrin, (MnTPPBrx(OAc) (x = 0, 2, 4, 6 and 8)) is reported. Although, the maximum conversion was achieved in the case of MnTPPBr4(OAc), little difference was found between the catalytic activity of MnTPP(OAc), MnTPPBr2(OAc) and MnTPPBr4(OAc). MnTPPBr8(OAc) showed an unusually very low catalytic efficiency compared to the other manganese porphyrins. The presence of small amounts of acetic acid was shown to have significant effect on the total conversion and the oxidative stability of the catalyst.Catalytic activity of the manganese complexes of a series of non-, partially and fully β-brominated meso-tetraphenylporphyrin, (MnTPPBrx(OAc) (x = 0, 2, 4, 6 and 8)) for the oxidation of sulfides to sulfoxides with UHP in the presence of ImH has been studied.Display Omitted
Keywords: Oxidation; Sulfides; Urea hydrogen peroxide (UHP); Manganese porphyrin;

Synthesis, structure and magnetic properties of heterometallic coordination polymers constructed from Cu (II)/Mn (II), H2bdc and H4btec by Hui Hu; Rui-Hong Zhang; Fan Yang; Yan-Hong Zhang; Qing-Lun Wang; Guang-Ming Yang (87-91).
Three novel heterometallic coordination polymers [(CuLH2O)2MnCuL](ClO4)2 (1), [CuLMn(bdc0.5)2(H2O)] (2) and [CuLMn(btec)0.5EtOH] (3) have been synthesized using the mononuclear ligand CuL (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,10,12-trimethyl-1,4,8,11-tetraazacyclo-tetradeca-7,12-diene; H2bdc = p-phthalic acid; H4btec = 1,2,4,5-benzenetetracarboxylic acid) as a precursor. Single-crystal X-ray diffraction reveals that the configuration of complexes 13 is tetranuclear compound with connectivity 0D, one-dimensional (1D) chain and two-dimensional (2D) layer, respectively. For complex 2, the adjacent 1D chains are interlinked mutually through the hydrogen bonds between the carboxylate groups of the H2bdc ligands and coordinated water molecules, extending the 1D chains into hydrogen-bonded 2D layers. Complex 3 exhibits a 2D sheet structure formed by the H4btec ligands. The magnetic studies of complex 1 show overall antiferromagnetic interactions between the Cu (II) and Mn (II) ions.Three novel heterometallic coordination polymers [(CuLH2O)2MnCuL](ClO4)2 (1), [CuLMn(bdc0.5)2(H2O)] (2) and [CuLMn(btec)0.5EtOH] (3) have been synthesized using the mononuclear ligand CuL (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,10,12-trimethyl-1,4,8,11-tetraazacyclo-tetradeca-7,12-diene; H2bdc = p-phthalic acid; H4btec = 1,2,4,5-benzenetetracarboxylic acid) as a precursor. Single-crystal X-ray diffraction reveals that the configuration of complexes 1–3 is tetranuclear compound with connectivity 0D, one-dimensional (1D) chain and two-dimensional (2D) layer, respectively. Moreover, the magnetic properties of complex 1 were investigated.Display Omitted
Keywords: Macrocyclic mononuclear ligand; Tetranuclear complex; 1D chain and 2D layer complexes; Crystal structures; Magnetic studies;

Auxiliary ligand-assisted structural diversities of two coordination polymers with 2-hydroxyquinoline-4-carboxylic acid by Dasarath Mal; Rupam Sen; Paula Brandao; Fanian Shi; Rute A.S. Ferreira; Zhi Lin (92-96).
The solvothermal reactions of Cd(NO3)2∙ 6H2O with 2-hydroxyquinoline-4-carboxylic acid (H2hqc) and 4,4′-bipyridine (bpy) or trans-1,2-bi(4-pyridyl)ethylene (bpe) afforded two coordination polymers [Cd(H-hqc)2(bpy)(H2O)2]n (1) and [Cd(H-hqc)2(bpe)0.5]n (2), respectively. The bipyridine based auxiliary ligands such as bpy and bpe were selected in order to analyze the effect of the length of auxiliary ligands on the formation of coordination polymers. Compounds 1 and 2 were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 shows a one-dimensional (1D) chain structure with linear topology while compound 2 shows 2D network with 3,6-c binodal net, having point symbol {32.4}{34.43.52.65.7} and vertex symbol [3.3.6(2)][3.3.3.3.6(2).6(2).6(2).6(2).6(2).*.*.*.*.*.*]. The results show that the spacer lengths of N-donor ligands do effect the topological structures of cadmium(II) coordination polymers.The structural diversity of cadmium coordination polymers based on 2-hydroxyquinoline-4-carboxylic acid may be controlled with the help of auxiliary ligands.Display Omitted
Keywords: Solvothermal synthesis; Cadmium; Coordination polymer; Spacer length effect;

Four chiral Ag(I) complexes with dual chiral components have been synthesized by using a series of (1R,2R)-N 1,N 2-bis(pyridinylmethyl)cyclohexane-1,2-diamine ligands with different N-positions of pyridyl rings. The circular dichroism (CD) spectra and second-harmonic generation (SHG) efficiency measurements confirmed that they are of structural chirality in the bulk samples. The luminescence properties indicated that they may have potential applications as optical materials. The formation of discrete mononuclear and binuclear complexes and one-dimensional chains may be attributed to positional isomerism of the ligands.Four chiral Ag(I) complexes with dual chiral components have been synthesized by using a series of chiral ligands with different N-positions of pyridyl rings. Their CD spectra and SHG efficiency have been measured. The luminescence properties have been also discussed.Display Omitted
Keywords: Ag(I) complex; Dual chiral component; Second-harmonic generation; Luminescence;

Solvent-induced supramolecular isomerism in homochiral silver benzimidazolates by Xun-Gao Liu; Yan-Ying Wang; Ying-Ying Hu; Zhi-Guo Gu; Liang Shen (103-107).
Two pairs of enantiomers R -[Ag4(hebim)4] · 3DMAC ( R-1), S -[Ag4(hebim)4] · 3DMAC ( S-1), R -[Ag(hebim)] ( R-2) and S -[Ag(hebim)] ( S-2) [Hhebim = 2-(1-hydroxyethyl) benzimidazole] are reported. Complexes 1 and 2 are supramolecular isomers induced by solvent and are second harmonic generation (SHG) active. In addition, solid-state luminescent properties of 1 and 2 were investigated at room temperature.Supramolecular isomers of homochiral silver benzimidazolates R-[Ag4(hebim)4] · 3DMAC ( R-1), S- [Ag4(hebim)4] · 3DMAC ( S-1), R-[Ag(hebim)] ( R-2) and S-[Ag(hebim)] ( S-2) are synthesized in different solvent.Display Omitted
Keywords: Ag(I); Supramolecular isomerism; Second harmonic generation; Luminescence;

A mixed-addenda Nb/W polyoxometalate containing dimeric Dawson subunit: Synthesis, structure, and characterization by Yuanhang Ren; Yichen Hu; Yucheng Shan; Zuping Kong; Min Gu; Bin Yue; Heyong He (108-111).
A mixed-addenda Nb/W polyoxometalates, K4Na4[H6P2W12Nb4O59(NbO2)2]2  · 48H2O (1), has been isolated under acidic condition. The single crystal structural analysis showed that the six vacant sites of the lacunary {P2W12} precursor are occupied by six Nb atoms, two at the polar sites and four at the equatorial sites to form a {P2W12Nb6} mixed-addenda subunit. Two {P2W12Nb6} subunits are joined together in an inversion mode by two Nb–O–Nb bridges from the Nb atoms at equatorial sites to form a dimeric unit, which can be considered as a Nb12 core wrapped by two lacunary {P2W12} polyoxoanions. It is notable that the terminal peroxo groups bonded niobium atoms in the Nb12 core are only partially eliminated during the formation of the dimeric unit.By reaction of [Nb6O19]8 − and hexavacant [H2P2W12O48]12 − under acidic condition, a mixed-addenda Nb/W polyoxometalate, K4Na4[H6P2W12Nb4O59(NbO2)2]2  · 48H2O, was obtained. The polyoxoanion contains a dimeric structure which is constructed by joining two {P2W12Nb6} monomers through two Nb–O–Nb bridges. The peroxo groups of the {P2W12Nb6} monomers were partial eliminated during the formation of the dimeric structure. The electrochemical property of the title compound was studied by CV and its electrochemical reduction of nitrite was also evaluated.Display Omitted
Keywords: Polyoxometalates; Nb/W mixed-addenda; Dawson type; Dimeric unit;

A novel six-coordinate ruthenium(II) complex 1, formulated as [Ru(bpy)2Lb]PF6⋅ C2H5OH (bpy = 2,2′-bipyridine), has been obtained and characterized. Ligand Lb in 1 comes from a chiral bis-Schiff-base ligand La which is condensed between sodium(I) salt of D- or L-phenylanine and terephthaldicarboxaldehyde. It is noted that ligand La undergoes partial C = N bond cleavage of Schiff-base unit forming a free aldehyde group at one end of phenyl ring, and an unusual proton migration, a C = N double-bond shift and subsequent nonchirality at the other end simultaneously in the presence of a ruthenium(II) ion.A novel ruthenium(II) complex 1 has been structurally characterized including a nonchiral ligand Lb formed from a chiral bis-Schiff-base compound with two stereogenic centers derived from D- or L-phenylalanine. In the process of Ru(II) ion complexation, a unique rearrangement takes place for ligand Lb involving the proton migration to cause the shift of a C = N double bond accompanied by the disappearance of a chiral center.Display Omitted
Keywords: Ruthenium(II) complex; Schiff-base ligand; α-Amino acid; C = N bond cleavage; Structural elucidation;

A novel lead(II) porous metal–organic framework constructed from a flexible bifunctional macrocyclic polyamine ligand by Xian-Dong Zhu; Ting-Xian Tao; Wei-Xiang Zhou; Fen-Hua Wang; Rong-Mei Liu; Li Liu; Ying-Qiang Fu (116-119).
A novel porous metal–organic framework [Pb2(TETA)]·6H2O (1) has been prepared by hydrothermal reaction of lead(II) with a flexible bifunctional macrocyclic ligand. The 1D Pb―O chains are cross-linked via the flexible macrocyclic rings of TETA4 − ligands in two different directions to form 3D framework with highly solvent accessible volume.A novel porous metal–organic framework [Pb2(TETA)]·6H2O (1) has been prepared by hydrothermal reaction of lead(II) with a flexible bifunctional macrocyclic ligand. The 1D Pb―O chains are cross-linked via the 14-membered macrocyclic rings of TETA4 − ligands in two different directions to form 3D framework with highly solvent accessible volume.Display Omitted
Keywords: Porous framework; Flexible macrocyclic ligand; Main group metal; Hydrothermal reaction;

Two new mononuclear complexes, [Co(L)2(H2O)2] (1) and [Ni(L)2(H2O)2] (2) (HL = 3-methyl-4-nitro-1-phenyl-5-pyrazolone), have been synthesized by the solvothermal reaction of Co(NO3)2 or Ni(NO3)2 with MPP (MPP = 3-methyl-1-phenyl-5-pyrazolone) in acetonitrile solution, and the ligand HL was generated in-situ through the nitration of MPP mediated by cobalt or nickel nitrate rather than mixture acids. Single crystal X-ray diffraction of 1 reveals that 1 consists of one Co(II), two L and two coordinated water molecules, and Co(II) adopts slightly octahedral geometry. Through intermolecular hydrogen bonding interactions, 1 presents two-dimensional network. Furthermore, the plausible nitration mechanism of MPP was also discussed.Two new complexes have been solvothermally synthesized. The ligand was generated in-situ and the plausable nitration mechanism of 3-methyl-1-phenyl-5-pyrazolone was discussed. Single crystal X-ray diffraction of 1 reveals that 1 was connected to form 2D network by hydrogen bonds.Display Omitted
Keywords: Nitration; In-situ synthesis; Solvothermal reaction; 3-methyl-1-phenyl-5-pyrazolone; Cobalt/nickel nitrate;

Solvothermal syntheses, crystal structures and luminescent properties of two new aromatic dicarboxylate indium coordination polymers by Guangpeng Zhou; Jiajun Han; Yulin Yang; Ruiqing Fan; Juan Li; Liqiu Fu; Yuan Zhang (124-128).
Two new indium coordination polymers formulated as [In(BPDA)(phen)Cl]n (1) and [In(BDC)(HBDC)·2DMF]n (2) (H2BPDA = 2,2′-biphenyldicarboxylic acid, C14H10O4; phen = 1,10-phenanthroline, C12H8N2; H2BDC = 1,3-benzenedicarboxylic acid, C8H6O4; DMF = N,N-dimethylformamide, C3H7NO) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, infrared (IR), thermal gravimetric analyses (TG) and luminescent studies. Molecular structural analyses reveal that complex 1 exhibits an indium-2,2′-biphenyldicarboxylate helical chained structure decorated with 1,10-phenanthroline, and complex 2 possesses a two-dimensional (2D) layered structure constructed by 1,3-benzenedicarboxylate ligands and InO6 octahedra, which has a (4,4) topological structure. Blue-green emission at 480 nm (λex  = 340 nm) for 1, intense blue-green emission at 492 nm, green emission at 535 nm, and yellow-green emission at 576 nm (λex  = 340 nm) for 2 are observed in the solid state at room temperature.Two new aromatic dicarboxylate indium coordination polymers have been solvothermally synthesized.Display Omitted
Keywords: Solvothermal synthesis; Crystal structure; Luminescence;

Synthesis and morphology research of framework Ti-rich TS-1 containing no extraframework Ti species in the presence of CO2 by Guowei Zhu; Lei Ni; Wei Qi; Shuang Ding; Xiaoxin Li; Runwei Wang; Shilun Qiu (129-132).
A new method to synthesis TS-1 has been developed using the carbon dioxide (CO2) as an alkalinity regulator that resulted in the increased framework Ti contents. The prepared catalyst had a Si/Ti ratio as low as 40 in contrast to the ratio of 56 prepared through conventional synthesis. The twin crystals with the length of 2 μm were formed via introduction of CO2. The catalytic activity of TS-1 is remarkably enhanced compared with the conventional synthesis.SEM micrographs of (e) TS-1-e (SiO2/CO2  = 0.029).Display Omitted
Keywords: Alkalinity regulator; Framework Ti content; Crystal morphology;

A series of organotin carboxylates based on (E)-3-(3-nitrophenyl) acrylic acid (HL), namely {[Ph3SnL]·0.5C6H6}n (1), [(Ph3Sn)2O(L)(Ph3Sn)(L)]n (2) and [Bu2LSnOSnLBu2]2 (3), have been synthesized. All the complexes have been characterized by elemental analysis, IR, 1H NMR spectroscopy and X-ray diffraction analyses. The structural analyses show that complexes 12 adopt 1D polymeric chain structures generated by the bridging carboxylate ligands and the five-coordinated tin centers. The structure of complex 3 is centro-symmetric and features a central rhombus Sn2O2 unit with two additional tin atoms linked at the O atoms. In addition, the antitumor activity of complex 3 has been studied.This work reports on the synthesis and structure of three complexes {[Ph3SnL]·0.5C6H6}n (1), [(Ph3Sn)2O(L)(Ph3Sn)(L)]n (2) and [Bu2LSnOSnLBu2]2 (3), which have been characterized by elemental analysis, IR, 1H NMR spectroscopy and X-ray diffraction analyses.Display Omitted
Keywords: Organotin carboxylates; Synthesis; Crystal structure; Antitumor activity;

Hydrothermal reactions of CdCl2·2.5H2O with 2-amine-4,4′-bis(1-imidazolyl)-bibenzene (abimb) and 5-hydroxy-1,3-benzenedicarboxylic acid (5-HO-1,3-H2BDC) or 5-oxyacetate isophthalic acid (H3OAIP) afforded two 3D Cd(II) coordination polymers, [Cd(5-HO-1,3-BDC)(abimb)]n (1) and {[Cd3(OAIP)2(abimb)2(H2O)3]·H2O}n (2). Complexes 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 can be considered as having a 3D doubly pillared-layer framework constructed through 2D undulated (4,4) layers and abimb pillars. 2 exhibits a 3D pillared-layer framework derived from 2D (6,3) bilayers and abimb pillars. The Schläfli symbols for the two frameworks are (412  · 63) (1) and (62  · 84)2(65  · 8) (2), respectively. The thermal and photoluminescent properties of 1 and 2 were also investigated.Two 3D coordination polymers [Cd(5-HO-1,3-BDC)(abimb)]n and {[Cd3(OAIP)2(abimb)2(H2O)3]·H2O}n were generated from solvothermal reactions of CdCl2 with 2-amine-4,4′-bis(1-imidazolyl)-bibenzene (abimb) and 5-hydroxy-1,3-benzenedicarboxylic acid (5-HO-1,3-H2BDC) or 5-oxyacetate isophthalic acid (H3OAIP). Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Display Omitted
Keywords: Hydrothermal synthesis; Cadmium; Crystal structure; Coordination polymer; 2-Amine-4,4′-bis(1-imidazolyl)-bibenzene;

Functional polymeric nanoparticles with folic acid end-capped poly(ethylene glycol) (PEG) as the shell and an iridium(III) complex coupled with poly(4-vinylpyridine) (P4VP)/[Ir(pq)2] (pq = 2-phenylquinoline) as the core have been prepared through complexation of the pyridine moiety with [Ir(pq)2]2 + followed by dialysis against water. The nanoparticles with folic acid on the surface are capable of entering HeLa cells. It is significant that, after cellular internalization, the intracellular compound histidine can trigger release of the [Ir(pq)2]+ residue into the nucleus from the nanoparticles. This provides a new pathway for triggering the release of drugs from their carriers.Functional iridium(III) complex-based polymeric nanoparticles with folic acid on the surface were synthesized, and their cell interaction and intracellular trigger release were demonstrated by luminescent technique.Display Omitted
Keywords: Iridium(III) complex; Polymeric nanoparticles; Luminescent bioimaging; Drug release;

A three-dimensional non-interpenetrated porous metal–organic framework based on cationic 1-D chains by Jian-Liang Zhou; Yuan-Yuan Wang; Min-Jia Zhou; Ling Qin; Ming-Dao Zhang; Qing-Xiang Yang; He-Gen Zheng (148-150).
One novel non-interpenetrated three-dimensional metal–organic framework (MOF) {[Cu4(μ 3-OH)4(L)2]·DMF} n (1) (H2L = 4,4′-(phenylazanediyl)dibenzoic acid) has been synthesized. The compound 1 contains positively charged 1-D copper hydroxy chains. The chains are interconnected by deprotonated L ligands into a 3D framework. The optical and magnetic properties have been investigated.One novel non-interpenetrated three-dimensional compound {[Cu4(μ 3-OH)4(L)2]·DMF} n has been synthesized. The compound contains positively charged 1-D copper hydroxy chains. The optical and the magnetic properties have been investigated.Display Omitted
Keywords: Metal–organic framework; Non-interpenetrated; Copper chains; Magnetic property;

Arenedisulfonate-4d–4f 3D heterometallic coordination polymers constructed from 2,7-naphthalenedisulfonate and isonicotinic acid: Structure, luminescence, and magnetic properties by Wei-Ping Xie; Ning Wang; Yi Long; Xing-Rui Ran; Jin-Ying Gao; Chu-Jun Chen; Shan-Tang Yue; Yue-Peng Cai (151-156).
The first example of 3D heterometallic 4d–4f 2,7-naphthanlenedisulfonate compounds [LnAg2(2,7-NDS)(IN)3] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy(5); 2,7-NDS = 2,7-naphthanlenedisulfonate; IN = isonicotinic acid) has been synthesized via hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analyses, FT-IR spectroscopy, powder X-ray diffraction(PXRD) and thermogravimetric analyses (TGA). X-Ray structural analysis reveals that compounds 15 exhibit same well-organized 3D coordination frameworks that are built up by 2D elliptical cylinder shaped [LnAg2(2,7-NDS)(IN)3] layers which are constructed by 1D anionic chains [Ln(2,7-NDS)(IN)3]2 − linking the adjacent Ag(I) ions, and [LnAg(μ2-O)2] units, possessing a 7-connected topology with the Schläfli symbol of {33;411;56;6}. Furthermore, the luminescence properties of compounds 2 and 4 and the magnetic properties of compounds 3 and 5 were investigated.The adjacent elliptical cylinder shaped 2D layers were assembled into 3D coordination frameworks by [SmAg(μ2-O)2] units. (The IN–Ag–IN bridges were omitted for clarity).Display Omitted
Keywords: 4d–4f coordination polymers; Topology; Luminescence; Magnetism;

The paper presents the synthesis of complex combinations of Cu(II), Zn(II) and Ni(II) with Schiff bases obtained by the condensation reaction of diphenylglyoxal with 1-amino-4-nitrobenzene (L1)/1-amino-4-chlorobenzene (L2)/p-anisidine (L3) as the main ligand and 1,10-phenanthroline as the co-ligand respectively. The characterization of newly formed complexes has been done by spectral and molar conductivity studies. The bioefficacy of the ligands and their complexes have been examined against the growth of bacteria and fungi in vitro to evaluate their antimicrobial potential. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. X-ray powder diffraction illustrates that the complexes have crystalline nature. The effect of the metal complexes on DNA is carried out by pUC19 DNA agarose gel electrophoresis at 50 V for 2 h. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents.The synthesized novel bio-active metal complexes possess a broad spectrum of activity and open the promise of finding new clinically effective antimicrobial compounds. They are good intercalators, laying the foundation for the rational design of new useful DNA probes and effective inorganic complex nucleases.Display Omitted
Keywords: XRD; Mixed ligand complexes; Antibacterial activity; DNA binding; DNA cleavage; 1,10-Phenanthroline complexes;

The syntheses of metal-free phthalocyanine 3 and metallophthalocyanines 4 and 5 with four 12-membered dithiadiaza macrocycles containing piperazine moiety on peripheral position have been accomplished by cyclotetramerization of 1,4-bis(2-(4,5-dicyano-1,2-pheylene)sulfanediyl)piperazine-2,5-dione 2. The formation of macrocycle containing piperazine subunit 2 did not require a high dilution technique or template effect and was performed by the reaction of 1 containing N-substituted 2-chloroamide moiety and sodium hydroxide in DMF. Metal-free phthalocyanine and metallophthalocyanines showed the enhanced solubility in organic solvents. These new compounds were characterized by a combination of elemental analysis and 1H NMR, 13C NMR, IR, UV–vis and MS spectral data.The present paper reports, for the first time the synthesis and characterization of metal-free and metallophthalocyanines substituted by four macrocycles containing piperazine moiety on peripheral positions. A convenient, one-pot procedure is described for the synthesis of the macrocycle containing piperazine moiety based on the mild condensation between two N-substituted 2-chloroamides.Display Omitted
Keywords: Macrocycle; Nitrogen–sulfur mixed donor; Metal-free phthalocyanine; Metallophthalocyanine; Piperazine; Transition metal;

Synthesis, structure and properties of a new noncentrosymmetric aluminoborate by Qin Meng; Guo-Ming Wang; Bai-Feng Yang; Huan He; Guo-Yu Yang (168-171).
A new noncentrosymmetric aluminoborate (H2TETA)[Al(B5O10)] (1), has been solvothermally synthesized by using triethylenetetramine (TETA) as the structure-directing agent. Single-crystal X-ray diffraction analysis reveals that the compound crystallizes in the orthorhombic space group Pna21 with unit cell parameters a  = 12.9696(9) Å, b  = 17.0035(8) Å, c  = 7.3660(5) Å, V  = 1624.41(18) Å3 and Z  = 4. Its structure consists of AlO4 tetrahedra and B5O10 clusters and possesses 8-, 11- and 14-ring channels with sra topology. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits moderate SHG signals approximately 1.5 times that of KH2PO4 (KDP).A new acentric aluminoborate (H2TETA)[Al(B5O10)] has been solvothermally synthesized and characterized, in which the AlO4 tetrahedra and B5O10 clusters alternately link to form a 3D framework with 8-/11-/14-ring channels, showing good SHG signals approximately 1.5 times that of KDP.Display Omitted
Keywords: Aluminoborate; Nonlinear optical; Solvothermal synthesis; Crystal structure;

Structure and magnetic properties of A Cu(II) coordination polymer supported by a tetrapodal Schiff base ligand by Guang-Qi Jiang; Shao-Jie Li; Yun-Qian Zhang; Qian-Jun Zhang (172-175).
A Cu(II) Schiff base coordination polymer, {[Cu3L(μ 2 -NO3)2·(H2O)2].3H2O}n, is readily prepared by complexation of the tetrapodal Schiff base, H4L (H4L = 1,1,1,1-tetrakis[(salicylaldimino)methyl]methane), with cupric nitrate trihydrate. It has been demonstrated that the coordination polymer consists of linear trinuclear Cu(II) entities, and displays a cooperative coordination mode for nitrate anions, coordinated water molecules, and Schiff base ligands to Cu(II) ions. In addition, variable-temperature magnetic susceptibility measurements reveal a strong antiferromagnetic coupling interaction between adjacent copper(II) ions with large J value of − 289.66 cm− 1.The perspective view of the segment of the Cu(II) Schiff base coordination polymer.Display Omitted
Keywords: Schiff base; Coordination polymer; Magnetic property;

A novel 3D self-catenated coordination polymer with multiform helical chains by Yu-Hui Luo; Ling-Ling Gu; Xiao-Yang Yu; Feng-Xia Yue; Xin Chen; Hong Zhang (176-180).
A novel noncentrosymmetric coordination polymer, namely, [Cd2L(H2O)2]·solvent (1) (H4L = tetrakis[4-(carboxyphenyl)oxamethyl]methane acid), has been successfully solvothermally synthesized and characterized by signal-crystal X-ray diffraction, IR spectra, element analysis, powder X-ray diffraction and thermogravimetric analysis. The structure study shows that 1 exhibits a 3D framework based on 1D carboxylate-metal chains. Furthermore, 1 contains three types of helical chains along the c axis. From a topological perspective, 1 can be reduced to a new self-catenated binodal (4,6)-connected (66)(615) topology. In addition, the second-order nonlinear optical and fluorescent properties of 1 have also been investigated.A novel NLO active coordination polymer has been synthesized under solvothermal condition. The self-catenated noncentrosymmetric framework contains three types of helical chains.Display Omitted
Keywords: Self-catenated; Multiform helical chains; Second-order nonlinear optical; Fluorescent property;

Synthesis, structure, and surface photovoltage property of two new cobalt (II) phosphonates with 2D layered structure by Lu-Lu Dai; Cui-Ying Huang; Rui Li; Zhen-Gang Sun; Cheng-Qi Jiao; Yan-Yu Zhu; Shao-Ping Shi; Wei Zhou (181-186).
Two new cobalt phosphonates, [enH2]0.5[Co(HL)(H2O)] · H2O (1) and [Co2(HL)(H2L)2] · 2NH(CH3)2  · 3H2O (2) (H3L = 2-hydroxyphosphonoacetic acid; en = ethylenediamine), have been synthesized under hydrothermal conditions and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. For compound 1, Co(II) atoms are octahedrally coordinated. The CoO6 octahedra and CPO3 tetrahedra are linked by HL2 − into a 2D layered structure in the bc-plane. The ethylenediamine molecules and solvate water molecules are located between two adjacent layers. The structure of compound 2 composed of Co1O6 and Co2O6 octahedra via bridging phosphonate ligands leads to a 2D layered structure with one-dimensional channel system along c-axis direction. The dimethylamine molecules and solvate water molecules are located between two adjacent layers. The surface photovoltage properties of compounds 1 and 2 have also been studied.Two new cobalt phosphonates with a 2D layered structure, [enH2]0.5[Co(HL)(H2O)] · H2O (1) and [Co2(HL)(H2L)2] · 2NH(CH3)2  · 3H2O (2) have been synthesized under hydrothermal conditions by using the 2-hydroxyphosphonoacetic acid as ligand. The surface photovoltage properties of compounds 1 and 2 have also been studied.Display Omitted
Keywords: Metal phosphonates; Crystal structure; Surface photovoltage property; Cobalt;

A novel 3D chiral complex, [Zn(adi)0.5(imb)] n (1) (Himb = 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole, H2adi = adipic acid) has been synthesized by solvothermal technique. X-ray diffraction analysis indicates that complex 1 consists of two kinds of channels with left-handed helical chains and one kind of zigzag chains. The channels and chains are connected through sharing Zn(II) centers to generate a 3D chiral complex. The TG analysis shows that complex 1 possesses great thermal stability. The fluorescence property of complex 1 has been measured in the solid-state at room temperature.Display Omitted
Keywords: Zn(II)-complex; Chirality; Thermostability; Fluorescence;

Two novel tetranuclear zinc(II) clusters with different topological structures: Crystal structures and luminescence properties by Wei Sun; Xiao-Ting Qin; Guo-Nan Zhang; Shuai Ding; Yan-Qin Wang; Zhi-Liang Liu (190-193).
Two novel tetranuclear zinc(II) clusters with different topological structures have been synthesized by using Zn(ClO4)2·6H2O, sodium azide and potentially multidentate Schiff base ligands containing different substituent groups. The two complexes have been characterized by elemental analysis, IR, single crystal X-ray diffraction and fluorescence studies. Structural studies reveal that [Zn4(HL1)41,1-N3)2(N3)2] (1) is a linear tetranuclear cluster whereas [Zn4(HL2)41,1-N3)4] (2) is a square-planar tetranuclear cluster. Both two complexes display intraligand (π → π*) fluorescence. Due to the heavy atom effect which increases the probability for intersystem crossing to the triplet state, the fluorescence intensity of complex 2 is much lower than that of complex 1.Two new Zn(II) complexes have been successfully synthesized under the identical experimental conditions. Due to the different types of R substituents in Schiff base ligands, complexes 1 and 2 exhibit linear and square-planar tetranuclear structures respectively. The fluorescence properties of these two complexes have also been investigated.Display Omitted
Keywords: Tetranuclear zinc(II) clusters; Schiff base ligands; Crystal structures; Luminescence properties;

Hydrothermal reactions of Cd(OAc)2  · 2H2O with 2,2′-azodibenzoic acid (H2L) and three N-donor ancillary ligands in MeOH/H2O at 120 °C gave rise to three cadmium(II) coordination polymers [CdL(bpy)] n (1), {[Cd4L4(bpe)(H2O)2] · 2H2O} n (2) and [CdL(bpp)] n (3) [bpy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene, bpp = 1,3-bis(4-pyridyl)propane]. Structural analysis reveals that compound 1 possesses a novel three-fold interpenetrating diamondoid framework constructed by linking Cd centers with L and pillared bpy ligands. Compound 2 comprises a 3D network with a rare Schläfli symbol of (446581)(4462), the 3D structure is built from 2D [CdL2] n nets and pillared bpe ligands. Compound 3 exhibits the same 66 topology with that of 1. Such a 3D architecture contains 1D helical [Cd(bpp)] n chains and [CdL] n chains along the a axis and b axis, respectively. The structural differences among 13 indicate that the N-donor ancillary ligands have significant effects on the formation of the final architectures. Photoluminescent properties of 13 in solid state were also investigated.Three new cadmium(II) coordination polymers with novel 3D structures have been successfully synthesized by assembly of flexible 2,2′-azodibenzoic acid (H2L) with three N-donor auxiliary ligands (bpy, bpe, bpp). The effects of auxiliary ligand have been discussed and the spectroscopic properties of these complexes were also studied.Display Omitted
Keywords: N-donor ancillary ligands; 2,2′-Azodibenzoic acid; Cd(II) coordination polymers; Structural diversities; Photoluminescent properties;

Spectral, thermal and structural studies of an acetate bridged polymeric cadmium(II) complex: Poly[aqua(μ-acetato)(4-aminobenzoato)cadmium(II) monohydrate] by Sunalya M. Roy; M.R. Sudarsanakumar; S. Suma; M.R. Prathapachandra Kurup; V.S. Dhanya; Remya M. Nair (200-204).
X-ray quality single crystals of [Cd(CH3COO)(paba)(H2O)]·H2O (Hpaba = 4-aminobenzoic acid) were grown by gel diffusion technique. The grown crystals are characterized by CHN analysis, Fourier Transform Infrared (FT-IR) and UV–visible spectral studies and thermogravimetry (TG). The crystalline nature of the compound was confirmed by powder X-ray diffraction studies. The structure of the grown crystal was determined by single crystal X-ray diffraction technique. The compound crystallizes in monoclinic space group P21/n and is having a polymeric structure. The porous nature of the compound is also evident from the structural studies. The fluorescent properties of the ligand and the compound were also investigated.Single crystals of [Cd(CH3COO)(paba)H2O]·H2O (Hpaba = 4-aminobenzoic acid) were grown by gel diffusion method. X-ray diffraction studies revealed that the compound crystallizes in a monoclinic space group P21/n and is a three dimensional metal–organic framework. Structural studies confirmed the porous nature of the framework.Display Omitted
Keywords: Crystal structure; Gel diffusion; X-ray diffraction; Fluorescence; Thermogravimetry; Spectroscopy;

Temperature effect-driven assembly of [CunXn]-based coordination polymers from CuX and 1,4-bis(imidazol-1-yl)butane by Ming Dai; Zhou Yang; Chun-Yan Ni; Hong Yu; Yang Chen; Hong-Xi Li; Zhi-Gang Ren; Jian-Ping Lang (205-210).
Three [Cu n X n ]-based (X = Br, I) coordination polymers, {[Cu2(μ-I)2(bimb)2]·iodobenzene} n (1), {[Cu43-I)4(bimb)2][Cu2(μ-I)2(bimb)]} n (2) and {[Cu2Br(bimb)2]Br} n (3) were prepared from solvothermal reactions of CuX (X = I, Br) with 1,4-bis(imidazol-1-yl)butane (bimb) at different temperatures. These compounds were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 contains a rhombic [Cu2(μ-I)2] dimer that acts as a planar four-connected node to link four equivalent ones via bimb bridges to form a 2D (4,4) network. Each layer is further stacked by π–π interactions to form a 3D structure with 1D rhombic channels occupied by the guest iodobenzene molecules. Compound 2 consists of [Cu2(μ-I)2] dimers and [Cu43-I)4] tetramers which are interconnected by bimb bridges to generate another 2D network. Compound 3 contains [Cu2Br(bimb)2]+ cations that are linked by bimb ligands to form a 1D cationic chain. We also investigated the solid state photoluminescent properties of 13 at ambient temperature. The results provide an interesting insight into how reaction temperatures exert a great effect on the assembly of [CunXn]-based coordination polymers.Three [Cu2(μ-I)2]- or [Cu43-I)4]-based coordination polymers, {[Cu2(μ-I)2(bimb)2]·iodobenzene} n , {[Cu43-I)4(bimb)2][Cu2(μ-I)2(bimb)]} n and {[Cu2Br(bimb)2]Br} n were prepared from solvothermal reactions of CuX (X = I, Br) with 1,4-bis(imidazol-1-yl)butane (bimb) at different temperatures. These compounds were characterized by elemental analysis, IR, and single crystal X-ray diffraction and their luminescent properties were investigated.Display Omitted
Keywords: Temperature effects; Copper halide; Coordination polymer; Solvothermal reactions; Crystal structures; 1,4-Bis(imidazol-1-yl)butane;

Self-assembly, electrochemistry and magnetic behaviors of cobalt complexes with featuring imidazole–tripodal ligand by Yan An; Xiao-Feng Li; Jing-Jia Sun; Shi-Fang Tong; Hong Yang; Shi-Ping Yang; Li-Hua Dong; Yan-Sheng Yin (211-214).
The coordination chemistry of imidazole–tripodal ligand N,N-bis(2-(1-methylimidazolyl)methyl)glycine (HL) has been studied with cobalt (II). Single-crystal X-ray analysis showed that the mononuclear complex [CoLCl] (1) could further act as the charge-negative metalloligand to assemble a heptanuclear complex of Co[CoLCl]6(NO3)2 (2) through the bridge linking of carboxylato O of L and the cooperation of the central metal ions. The electrochemical and magnetic properties were explored.The construction of mononuclear or polynuclear complex of Co(II) with an unsymmetrical imidazole–tripodal ligand could be controlled by altering the counter anions.Display Omitted
Keywords: Imidazole–tripodal ligand; Cobalt complex; Self-assembly; Electrochemical property; Magnetic property;

Novel Bi-based iodate photocatalysts with high photocatalytic activity by Hongwei Huang; Ying He; Ran He; Xingxing Jiang; Zheshuai Lin; Yihe Zhang; Shichao Wang (215-219).
Two novel Bi-based iodates BiIO4 and Bi(IO3)3 with nonbonding layered structures were successfully synthesized via a facile hydrothermal method. The as-prepared samples were characterized by XRD, SEM and DRS. Their optical band gaps and energy levels have been determined, which were also confirmed by the first principle calculations. BiIO4 and Bi(IO3)3 have an indirect and direct transition optical band-gap of 2.94 and 3.58 eV, respectively. The photocatalytic activities of the samples were determined by oxidative decomposition of methyl orange (MO) in aqueous solution. The results revealed that BiIO4 and Bi(IO3)3 display high photocatalytic activity, much better than that of Bi-based photocatalyst Bi2O2CO3. Especially, the photocatalytic efficiency of BiIO4 is about 2.2 times higher than that of commercial TiO2 (P25), though the BET surface is just 1/20 of that of P25. The layered structure should be responsible for the hole–electron separation and transport of charge.The iodates BiIO4 and Bi(IO3)3 with nonbonding layered structures were found to be novel photocatalysts and exhibit excellent photocatalytic activity.Display Omitted
Keywords: Bi-based; Iodates; Photocatalysis; Layered structure; Band gap;

A novel 3D silver iodide metal–organic framework {[Ag14I16(HDABCO)2]·(DABCO)}n (DABCO = 1,4-diazabicyclo[2.2.2]octane) (1) has been synthesized solvothermally. In this compound, a [Ag14I16]2 − anion cluster was formed by twelve AgI4 tetrahedra and two AgI3 triangles by sharing their edges, in which its charge is compensated by two mono-protoned HDABCO+. Each [Ag14I16]2 − cluster connects to six neighboring clusters by sharing corner I ions between the AgI4 tetrahedra, resulting in a 3D framework. The compound 1 displays intense fluorescence emission with maximum at 400 nm and 465 nm upon 310 nm excitation at room temperature.A novel 3D silver iodide metal–organic framework {[Ag14I16(HDABCO)2]·(DABCO)}n has been synthesized. The compound exhibits a 3D open framework constructed from [Ag14I16]2 − anion cluster, and two monoprotonated HDABCO+ ligands coordinated to Ag+ balance the charge. In addition, the compound exhibits strong fluorescence and thermal stability.Display Omitted
Keywords: Coordination polymer; Silver iodide anion cluster; Crystal structure; Fluorescence property; Thermal stability;