Inorganic Chemistry Communications (v.14, #5)

Contents List (iii-xiv).

Synthesis, structure and XPS of a novel two-dimensional CuII–EuIII heterometallic–organic framework by Yun-Zhi Tang; Yan-Ming Yang; Xiao-Wei Wang; Qian Zhang; He-Rui Wen (613-617).
Hydrothermal reaction of Eu2O3, CuI, 2, 2′-bipyridine-5, 5′-dicarboxylic acid and 2, 2′-bipyridine in the presence of ethanol and water affords a new 4f–3d heterometallic coordination polymer {[EuCu(bpdc)2·(H2O)4 I)]·2H2O}n (1), (H2bpdc = 2, 2′-bipyridine-5, 5′-dicarboxylic acid). Compound 1 was structurally characterized by elemental analysis, FT-IR spectroscopy, single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and luminescence measurement. Single-crystal X-ray diffraction analysis reveals that the heterometallic polymer is interconnected by Eu3+ through carboxylic groups to produce a linear 1D structure along a direction, then through Cu2+ chelating double nitrogen atoms of bpdc2− ligand along b direction to form a 2D (two-dimensional) CuII–EuIII heterometallic–organic framework. X-ray photoelectron spectroscopies (XPS) confirm that chemical valences of Eu and Cu are + 3 and + 2 respectively. The fluorescent intensity change between H2bpdc ligand and compound 1 reveals a radical static quenching effect from CuII ions.Single-crystal X-ray diffraction analysis reveals that the heterometallic polymer is interconnected by Eu3+ through carboxylic groups to produce a linear 1D structure along a direction, then through Cu2+ chelating double nitrogen atoms of bpdc2− ligand along b direction to form a 2D CuII–EuIII heterometallic–organic framework. X-ray photoelectron spectroscopies (XPS) confirm that chemical valences of Eu and Cu ions are + 3 and + 2 respectively.Display Omitted► The structure of title compound is a novel two-dimensional CuII–EuIII heterometallic–organic framework. ► There is no EuIII–CuII heterometallic organic framework containing iodine ion which has been reported before. ► The oxidation state of Cu before and after reaction is + 1 and + 2 respectively indicating a redox reaction happened during this process. ► XPS (X-ray photoelectron spectroscopy) investigation of crystallizing samples was carried out to elucidate the electronic states for the title compound.
Keywords: Heterometallic polymer; Crystal structure; Hydrothermal synthesis;

The new Schiff base ligand 2-(2-hydroxy-1, 2-diphenylethylideneamino) benzoic acid [HL] and its Co(II), Ni(II) and Cu(II) metal complexes were synthesized. The ligand and metal complexes were characterized by elemental analysis, UV-visible, IR, 1H NMR spectroscopy, thermal studies and magnetic susceptibility measurement. The ligand [HL] was synthesized by condensation of benzoin and 2-amino benzoic acid. On the basis of electronic spectral data and magnetic susceptibility measurement the octahedral geometry has been proposed for Cu(II), Ni(II) and Co(II) complexes. The ligand and metal (II) complexes were also screened for their antimicrobial activity against microorganisms Staphylococcus aureus and Pseudomonas aeruginosa and antifungal activity against the fungi Candida albicans and Aspergillus niger. 2-(2-Hydroxy 1,2-dipheylethylideneamino) benzoic acid (HL) and its Cu(II), Co(II) and Ni(II) complexes were synthesized and characterized on the basis of Elemental analysis, IR, UV–visible,1H NMR, spectral studies, magnetic susceptibility, thermal analysis. The ligand and its Cu(II), Ni(II) and Co(II) complexes were screened for their antibacterial and antifungal activity by using minimum inhibitory concentrations (MICs) method.Display Omitted► Synthesis, characterization and antimicrobial activity of new cobalt (II), nickel (II) and copper (II) complexes with 2-(2-hydroxy-1, 2-diphenylethylideneamino) benzoic acid. ► 2-(2-Hydroxy 1,2-dipheylethylideneamino) benzoic acid (HL) and its Cu(II), Co(II) and Ni(II) complexes were synthesized and characterized on the basis of Elemental analysis, IR, UV–visible,1H NMR, spectral 23 studies, magnetic susceptibility, thermal analysis. ► The ligand and its Cu (II), Ni (II) and Co (II) complexes were screened for their antibacterial and antifungal activity by using minimum inhibitory concentrations (MICs) method.
Keywords: Transition metal complexes; 2-Amino benzoic acid; Schiff base; Antifungal and antibacterial activity;

Two new CuI-phenanthrene-9-carbonitrile (phencn) based coordination polymers formulated with [CuI(phencn)] n (1) and [Cu2I2(phencn)] n (2) are easily accessible by the reaction of copper(I) iodide with phencn in different stoichiometric ratios of the reactants. 1 contains Cu2I2 double-stranded stair that can be regarded as two CuI zigzag single chains connected together via Cu―I bonds, while 2 consists of novel one-dimensional Cu6I6 hexagonal cage chain that can be conveniently described as two Cu2I2 double-stranded stairs connected together via Cu―I bonds. The monodentate phencn ligands regularly stack along both sides of the (CuI) n skeletons in 1 and 2. IR, elemental analysis and XRPD confirmed the phase purity of the bulk materials. The photoluminescent properties of 1 and 2 in the solid state at ambient temperature are also investigated.Syntheses, structures and photoluminescent properties of two new low-dimensional copper(I) iodide coordination polymers [CuI(phencn)] n (1) and [Cu2I2(phencn)] n (2) (phencn = phenanthrene-9-carbonitrile) are described in which Cu2I2 double-stranded stair and Cu6I6 hexagonal cage chain, supported by a monodentate ligand phenanthrene-9-carbonitrile, are revealed.Display Omitted► A comparative study of two new low-dimensional CuI coordination polymers is reported. ► The novel Cu2I2 stair and Cu6I6 hexagonal cage chain are found in complex 1 and 2. ► The stoichiometry of the reactants provides the structural diversity of complex 1 and 2. ► The mutual repulsion and steric hindrance of the phenanthrene rings is interesting. ► The photoluminescent properties of complex 1 and 2 are very well.
Keywords: Copper iodide; Photoluminescence; Crystal structure; Hexagonal cage chain;

Solvothermal treatments of (E)-1,3-diallyl-2-styryl-3  H -benzo[d]imidazol-1-ium bromide olefin ligand 1 and CuX (X═Br, 2 and X═Cl, 3) in the presence of methanol as solvent at 75 °C for 1 week offer organic–inorganic hybrid compound 2 and olefin–copper(I) compound 3. The conformation of olefin cation ligand affects the coordination of allyl group. Two allyl groups existing at different sides of benzoimidazole plane successfully coordinate to copper(I) centers to form olefin–copper(I) coordination compound 3, which shows two-dimensional structure of (4,4) network with [Cu6Cl4Br4]2− cluster nods. The dielectric measurement results show there is no dielectric anomaly observed within the temperature range of 120 K to 300 K for compound 3.Display Omitted► Solvothermal synthesis of olefin-copper(I) coordination compound. ► The conformation of organic ligand affects the formation of olefin-copper(I) coordination compound. ► Novel copper–halide cluster as node to construct 2D (4,4) net coordination polymer. ► High dielectric constant. ► Fluorescent influence.
Keywords: Solvothermal; Olefin–copper(I); Cluster; Dielectric; Ligand conformation;

A new luminous hexacoordinated coordination polymer of cadmium(II) containing benzidine and dicyanamide as bridging units by Smita Satapathi; Soumi Chattopadhyay; Kishalay Bhar; Sumitra Das; Ramachandran Krishna Kumar; Tapas Kumar Maji; Barindra Kumar Ghosh (632-635).
A neutral hexacoordinated 2D coordination polymer [Cd(bnzd)(dca)2]n (1) [bnzd = benzidine and dca = dicyanamide] is prepared using a one-pot reaction of the building units and characterized. X-ray structural analysis reveals each cadmium(II) center to adopt a distorted octahedral geometry with a CdN6 chromophore bound by two N atoms of two different bnzd and two sets of double μ1,5 dca units affording a 2D sheet structure with a (4,4) topology. In the crystalline state, multiple intermolecular N―H⋯N hydrogen bonds result in a 3D network structure. 1 displays intraligand 1(π–π) fluorescence in DMF solution at room temperature.A new photoluminous μ1,5 dicyanamide bridged 2D coordination polymer with (4,4) topology of cadmium(II) in concert with benzidine has been synthesized and characterized. Formation of 3D supramolecular architecture by intra- and intermolecular N―H⋯N hydrogen bonding has been discussed.Display Omitted► A hexacoordinated polymer [Cd(bnzd)(dca)2]n [bnzd = benzidine] is isolated. ► X-ray study shows 2D layer structure via EE bridging motifs of both bnzd and dca. ► Thermogravimetric analysis shows its thermal stability and decomposition pattern. ► The compound is an example of luminous material.
Keywords: Polymeric cadmium(II); Dicyanamide; Benzidine; X-ray structure; Luminescence;

Synthesis, characterization and urease inhibitory activity of oxovanadium(V) complexes with similar Schiff bases by Zhong-Lu You; Yong-Ming Cui; Yu-Ping Ma; Che Wang; Xiao-Shuang Zhou; Kun Li (636-640).
A series of structurally similar oxovanadium(V) complexes with analogous Schiff bases have been prepared and structurally characterized. The urease inhibitory activities of the complexes were investigated. The shorter the terminal groups of the Schiff base ligands are, the stronger the urease inhibitory activities of the oxovanadium(V) complexes.A series of structurally similar oxovanadium(V) complexes with analogous Schiff bases have been prepared and structurally characterized. The urease inhibitory activities of the complexes were investigated.Display Omitted► A series of oxovanadium(V) complexes with Schiff bases have been synthesized. ► The complexes have been characterized by elemental analyses, IR spectra, and single crystal X-ray diffraction. ► The complexes show from moderate to strong urease inhibitory activity. ► The molecular docking study of the complexes with urease was performed.
Keywords: Schiff base; Oxovanadium complex; Crystal structure; Urease inhibition;

The synthesis of new magnesium porphyrazines, peripherally substituted with 14-membered dioxa-dithia (O2S2) and tetrathia (S4) macrocycles has been accomplished by cyclotetramerization of (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzodioxadithia-cyclotetradecine-6,7-dicarbonitrile (3) or (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzotetrathiacyclotetradecine-6,7-dicarbonitrile (5) in the presence of magnesium butanolate. The precursors were prepared from disodium salt of dithiomaleonitrile and o-xylenebis(1-chloro-3-oxapentane) (2) or o-xylenebis(1-chloro-3-thiapentane) (4). The metal-free porphyrazines are obtained by the treatment of these magnesium porphyrazines with trifluoroacetic acid. These new compounds are characterized by a combination of elemental analysis and 1H, 13C NMR, IR, UV–vis and MS spectral data.New magnesium porphyrazines (6, 7) and metal-free porphyrazines (8, 9) containing four peripheral dioxa-dithia or tetrathia crown moieties have been synthesized by cyclotetramerization reaction of substitue dicarbodinitriles (3, 5).Display Omitted► Novel reactants, 7,12-benzo-6,15-dioxa-3,18-dithiacyclotetradec-1-en-1,2-dicarbodinitrile (O2S2) and 7,12-benzo-3,6,15,18-tetrathiacyclotetradec-1-en-1,2-dicarbodinitrile (S4) synthesized and characterized. ► Novel porphyrazinatomagnesium (MgPz) and metal free porphyrazine (H2Pz) containing four symmetrical dioxadithia (O2S2) macroycles at peripheral positions was synthesized. ► Novel MgPz and H2Pz containing four symmetrical tetrathia (S4) macroycles at peripheral positions was synthesized.
Keywords: Metalloporphyrazine; Metal-free porphyrazine; Dioxa-dithia macrocycle; Tetrathia macrocycle; Template effect; Magnesium;

A porous aluminum(III) metal-organic framework, [Al8(OH)15(H2O)3(btc)3]n, MIL-110, has been synthesized by hydrothermal method and characterized by elemental analyses, X-ray powder diffraction (XRD) and IR spectroscopy. MIL-110 (Al) was calcinated at different temperatures under air atmosphere to prepare Al2O3 and in another process MIL-110 (Al) nanoparticles were prepared by using oleic acid. The product of each step was characterized by scanning electron microscopy, X-ray powder diffraction (XRD) and energy-dispersive X-ray analysis (EDAX). This study demonstrates that the metal-organic frameworks may be suitable precursors for the simple one-pot preparation of nanoscale metal oxide materials with different and interesting morphologies.A porous aluminum(III) metal-organic framework, [Al8(OH)15(H2O)3(btc)3]n, MIL-110, has been synthesized by hydrothermal method and characterized by elemental analyses, X-ray powder diffraction (XRD) and IR spectroscopy. Two different methods were used for preparation of Al2O3 from MIL-110.Display Omitted► An Al(III) porous coordination polymer as a precursor. ► Synthesis of Al2O3 nano- particles from one porous coordination polymer. ► Synthesis of one Al(III) porous coordination polymer at nano-scale.
Keywords: Metal-organic framework; Thermal properties; Nano-materials; Aluminum(III);

In situ cleavage and coupling of sulfur-carbon (sp2) bond towards a two-dimensional mesh construction by Ning Yuan; Tianlu Sheng; Chongbin Tian; Shengmin Hu; Ruibiao Fu; Xintao Wu (649-653).
A novel coordination polymer [Ni(mdn)(H2O)2] (mdn  = 6,6’-mercaptodinicotinate) (1) has been prepared, and characterized by single-crystal X-ray diffraction along with powder XRD, Infrared spectrum, elemental analysis and magnetic analysis. Complex 1 displays an interesting two-dimensional wave-like mesh construction and further forms a three-dimensional supramolecular structure based on π∙∙∙π and C–H∙∙∙π stacking interactions. A rarely reported transition-metal-mediated in situ cleavage and coupling of sulfur-carbon (sp2) bond has been observed.Presented here is an unusual in situ cleavage and coupling of sulfur-carbon (sp2) bond towards a two-dimensional mesh construction. The mesh network further forms a three-dimensional supramolecular complex via intermolecular π∙∙∙π and C–H∙∙∙π stacking interactions.Display Omitted► An unusual in situ cleavage and coupling of sulfur-carbon (sp2) bond was found. ► The possible process of the in situ formation is illustrated in this work. ► This reaction would provide a new method for the formation of metal-organosulfides.
Keywords: Crystal structure; Nickel; Sulfur-carbon bond; In situ Reaction; Cleavage;

A new amide type bridging ligand, 1,5-bis{[(2′-(2-picolylaminoformyl))phenoxyl]methyl}naphthalene (L), and its complexes with lanthanide ions (Ln═Sm, Eu, Gd, Tb, and Dy) have been designed and assembled. The crystal structures of {[EuL(NO3)3(CH3OH)](H2O)}n and [TbL(NO3)3(CH3OH)]n display one-dimensional (1-D) zig-zag coordination polymeric chains. At the same time, the solid state luminescent properties of the Sm, Eu, Tb, and Dy complexes were investigated at room temperature. The complexes all exhibit characteristic luminescence emissions of the central metal ions under UV light excitation. The lowest triplet state energy level (T1) of the ligand indicates that the triplet state energy level of the ligand matches better to the resonance level of Tb(III) ion than other lanthanide ions.A series of luminescent one-dimensional zig-zag coordination polymers have been rationally assembled by the reaction of lanthanide nitrate and a new amide type bridging ligand 1,5-bis{[(2′-(2-picolylaminoformyl))phenoxyl]methyl}naphthalene.Display Omitted► A new amide type bridging lignd L and its lanthanide complexes were synthesized. ► The crystals of {[EuL(NO3)3(CH3OH)](H2O)}n and [TbL(NO3)3(CH3OH)]n were obtained. ► One-dimensional zig-zag lanthanide coordination polymers were designed and assembled. ► The complexes exhibited characteristic luminescence emissions of lanthanide ions. ► The fluorescence quantum yield of the Tb(III) complex is the strongest.
Keywords: Amide type bridging ligand; Lanthanide; Coordination polymers; Luminescent properties;

Efficient palladium-catalyzed Suzuki cross-coupling reaction with β-ketoamine ligands by Zong-Zhou Zhou; Feng-Shou Liu; Dong-Sheng Shen; Cheng Tan; Ling-Yan Luo (659-662).
A series of β-ketoamine ligands with different steric and electronic substituents on the backbone and with aniline moieties have been synthesized and characterized. In the presence of PdCl2, catalytic studies indicated that they are effective ligands for Suzuki cross-coupling of various aryl bromides with phenylboronic acid, under aerobic conditions.A series of β-ketoamine ligands were synthesized and employed in Suzuki cross-coupling reaction under aerobic conditions. The catalytic reaction revealed that the ligand with bulky and electron-donating group was most efficient, enabling a wide variety of aryl bromides to be coupled with phenylboronic acid in high yield.Display Omitted► β-ketoamine ligands applied in Suzuki cross-coupling reaction were prepared. ► The bulky and electron-donating groups on ligands are benefit for the reaction. ► Reaction conditions of the cross-coupling were optimized.
Keywords: β-ketoamine ligands; Backbone; Aniline moiety; Suzuki cross-coupling reaction;

Ionothermal synthesis, structure and optical properties of three new organic–inorganic hybrid imidazolium bromoplumbate complexes by Jing-Ping Niu; Quan-Guo Zhai; Jun-Hua Luo; Shu-Ni Li; Yu-Cheng Jiang; Man-Cheng Hu (663-666).
By heating imidazolium bromide-based ionic liquids with Pb(NO3)2 under ionothermal conditions, we have successfully generated three imidazolium bromoplumbates, namely, [(PMI)PbBr3] n (1), [(AMI)PbBr3] n (2) and [(HMI)PbBr3] n (3) (PMI = 1-propyl-3-methylimidazolium, AMI = 1-allyl-3-methylimidazolium, HMI = 1-hexyl-3-methylimidazolium). Compounds 13 are isomorphic and exhibit unusual supramolecular organization wherein dialkylimidazolium cations arrange themselves in a cylindrical fashion giving rise to channel structures, which are further occupied by the 1D zigzag [PbBr3] n inorganic chains. The UV–vis diffuse reflectance spectra and luminescence measurements indicate that all compounds are potential semiconductor and photoluminescence materials.Three imidazolium bromoplumbate organic–inorganic hybrid solids were obtained under ionothermal conditions and exhibit unusual supramolecular organization wherein dialkylimidazolium cations arrange themselves in a cylindrical fashion giving rise to channel structures, which are further occupied by the 1D zigzag [PbBr3] n inorganic chains.Display Omitted► Dialkyl-imidazolium bromide-based ionic liquids are utilized as solvent. ► Crystal structures for three imidazolium bromoplumbate hybrid solids. ► Strong blue photoluminescence generated from the zigzag [PbBr3]n chain. ► Three compounds are potential semiconductor materials.
Keywords: Ionothermal synthesis; Ionic liquids; Bromoplumbate; Optical properties;

We present here a new example of Cu–azido compound (L′)2[Cu7(N3)16] (1) synthesized using imidazolium-type cationic template in-situ obtained from metal-mediated cyclizations of 2-[(pyridin-2-ylmethylen)amino]ethanol. The compound possesses a rarely observed anionic Cu–azide layer, which consists of [Cu7(N3)16]2− anionic heptanuclear units extensively linked by end-on azido bridges. The molecular geometry results in ferromagnetic interactions within the Cu–azide heptanuclear unit. The title compound displays long-range antiferromagnetic ordering with Néel temperature being ca. 7.85 K.Display OmittedA Cu–azido layer compound (L′)2[Cu7(N3)16] (1) was in-situ synthesized obtained from metal-mediated cyclizations of 2-[(pyridin-2-ylmethylen)amino] ethanol.► The in-situ synthesis of this type of azido compound is novel. ► The linear heptnuclear azido-copper as repeated unit is seldom reported. ► The magnetic property is interesting for the coexistence of AF and FM interaction. ► Appropriate model to fit the magnetic data.
Keywords: Azido compound; Linear molecule; Crystal structure; Magnetic property;

An N-heterocyclic carbene palladium-based complex, cis-dibromo{1,1′-di[3,4,5-trimethoxybenzyl]-3,3′-butylenedibenzimidazol-2,2′-diylidene}palladium(II), has been synthesized and characterized by elemental analysis, IR spectroscopy and 1H- and 13C-NMR spectroscopy. The crystal and molecular structure of the title compound was determined by single-crystal X-ray diffraction. The title compound consists of a 1,1′-di[3,4,5-trimethoxybenzyl]-3,3′-butylenedibenzimidazole and two bromo ligands coordinated to a palladium atom in a distorted square-planar cis-system. Two benzoimidazole rings are connected to each other by a C4H8 bridge. The substituted benzimidazole ligand forms a bidentate chelate with palladium, bonding via the carbene carbon atoms. There are two independent molecules A and B in the asymmetric unit. The Pd―Br bonds are 2.4675(14) and 2.4601(13) Å, and the Pd―Ccarbene bonds are 1.985(9) and 1.986(9) Å for molecule A. Each A and B molecule is stabilized with intra- and inter-molecular hydrogen bonds and C―H…π interactions. The palladium–carbene complex was tested as a catalyst in the direct arylation of benzothiazole with arylbromides. The most suitable reaction conditions for the direct arylation of benzothiazole with arylbromides are NMP, K3PO4, Pd–NHC and 130 °C.A novel palladium(II) complex bearing N-heterocyclic carbenes has been synthesized by the reaction of bis(benzimidazolium) salt with the Pd(OAc)2 in dimethyl sulfoxide and characterized by elemental analyses, infrared, 1H and 13C NMR spectroscopy and single-crystal X-ray diffraction analysis. The catalytic studies on palladium(II) complex indicate that it is a potent catalyst for even milder reaction conditions such as amination or arylation of various azoles.Display Omitted► An N-heterocyclic carbene palladium-based complex has been synthesized. ► The crystal structure of complex was determined by single-crystal X-ray diffraction. ► There are two independent molecules A and B in the asymmetric unit. ► The complex was tested as a catalyst in the direct arylation of benzothiazole. ► The reaction conditions for the direct arylation are NMP, K3PO4, Pd-NHC and 130 °C.
Keywords: N-heterocyclic carbenes; Bidentate palladium complexes; Crystal structure; Arylation of benzothiazole; Palladium catalyst;

Simple and efficient: Gold nanoparticles from triphenylphosphane gold(I) carboxylates without addition of any further stabilizing and reducing agent by André Tuchscherer; Dieter Schaarschmidt; Steffen Schulze; Michael Hietschold; Heinrich Lang (676-678).
An innovative and straightforward methodology for the generation of gold nanoparticles (= NP) from [(Ph3P)-AuO2CCH2(OCH2CH2)2OCH3] without addition of any further stabilizing and reducing reagents is reported; particles of size 3–6 nm (average diameter 4 nm) with narrow size distribution are obtained.A straightforward, very efficient methodology for the generation and stabilization of gold nanoparticles (4 (+/-1) nm) of narrow size distribution by thermal decomposition of the “all-in-one precursor” (Ph3P)-AuO2CCH2(OCH2CH2)2OCH3 is reported; no reduction and stabilizing agents must be added.Display Omitted► An efficient and simple methodology for the generation of Au NPs is reported.. ► A novel “all-in-one” gold(I) precursor is prepared. ► No addition of further reducing and stabilizing agents for Au NP formation is needed. ► The size of NPs is temperature dependent.
Keywords: Gold; Nanoparticle; Thermolysis; Carboxylate;

Two isolated structural motifs in one crystal: One of which fills helical channels in another by Jia-Bin Li; Shuang-Quan Zang; Li-Hui Cao; Thomas C.W. Mak (679-682).
An unusual compound Zn1.5(Hsdpa)(bpy)1.5(H2O)4 (1) comprising two isolated coordination polymers has been obtained by hydrothermal reactions, in which helical channels of a 3D host framework A [Zn(Hsdpa)(bpy)(H2O)2] are filled with the guest infinite 1D polymer chains B [Zn0.5(bpy)0.5(H2O)2]+.Display Omitted► A 3D coordination polymer comprises two isolated coordination. ► Weak interactions between host and guest stabilize the structure. ► Helical voids of the host are filled by the 1D guest metal-organic polymers. ► The luminescent properties of d10 metal-organic polymers.
Keywords: Coordination polymer; Helical channel; Host framework; Guest polymer chain;

A new Ru(II) complex, [Ru(II)(bpy)2BIOQ][PF6]2, has been synthesized with bpy (bpy = 2,2′-bipyridine) as the first ligand and 2-(benzimidazol-2-yl)-8-octyloxyquinoline (BIOQ) as the second ligand. The Ru(II) complex features high thermal stability with a melting point of 299–300 °C and a decomposition temperature of 299 °C (onset). The photoluminescence spectrum of the complex in solid state exhibits a strong emission band at 450 nm.Display Omitted► The presence of octyloxy group can decrease the symmetry of the ligand and consequently the symmetry of the corresponding complex. ► The presence of octyloxy group in ligand can increase the lipophilicity of complex to improve its solubility inorganic solvents. ► This Ru(II) complex exhibits relatively high thermal stability with a high melting point and a high decomposition temperature.
Keywords: 8-octyloxyquinoline; Ruthenium complex; Photoluminescence spectrum; Thermal stability;

Ruthenium(II) cyclometallated complex containing para-chloroacetophenone thiosemicarbazone (L) of formula [Ru(L)(CO)(PPh3)2] has been synthesized and characterized by elemental and spectral analyses. The thiosemicarbazone ligand coordinates to ruthenium as a terdentate C, N, and S donor generating two five membered metallacycles. The crystal structure analysis of the complex [Ru(L)(CO)(PPh3)2] indicates the presence of a distorted octahedral geometry. The complex shows a quasi-reversible one electron oxidation (RuIII/RuII) at 0.78 V vs SCE. Further, the catalytic transfer hydrogenation of substituted acetophenones by the titled complex was carried out with conversions up to 99.3% in the presence of i-prOH/KOH.Ruthenium(II) cyclometallated complexes derived from C-H activation of thiosemicarbazone efficiently catalyzes a series of acetophenones and the maximum conversion was found to be 99.3%.Display Omitted► This work aims to generate air stable M-C bond ie, organometallic species. ► Synthesized complex has been characterized by spectral and analytical methods. ► Cyclometallation was achieved via C-H activation of TSC ligand by ruthenium complex. ► Transfer hydrogenation of acetophenones by ruthenium complex has been studied.
Keywords: Cyclometallation; X-ray structure; Redox behavior; Catalytic transfer hydrogenation;

A catalytic process for the selective oxidation of alcohols by copper (II) complexes by Dileep Ramakrishna; Badekai Ramachandra Bhat (690-693).
Novel copper (II)–N–(2-pyridyl)–N'–(5-R-salicylidene) hydrazine triphenylphosphine complexes have been synthesized and characterized. The complexes were effective in the catalytic oxidation of primary and secondary alcohols in presence of periodic acid (H5IO6) as oxidant. The oxidation reactions were carried out in acetonitrile. Electrochemical electron transfer study reveals CuII–CuI reduction in methanolic solutions. A mechanistic study of the above reactions has been proposed.A catalytic system consisting of copper–Schiff base-triphenylphosphine complex and periodic acid was effective in the selective oxidation of primary and secondary alcohols. The oxidation reactions were carried out in acetonitrile.Display Omitted► Copper (II)–Schiff base complexes with triphenylphosphine were effective in the oxidation of primary and secondary alcohols in acetonitrile medium in presence of periodic acid. ► Short reaction time of 30 min ► Reaction requires no external additives ► A variety of alcohols were selectively oxidized to their corresponding carbonyl compounds.
Keywords: Copper (II) complexes; Schiff base; Catalytic oxidation; Periodic acid;

A 3D hydrogen bonding framework of trinuclear Ni(II) complex in mixed ligands system: Structural and magnetic studies by Xiao-hua Chen; Qiong-jie Wu; Wei Lu; Ming-xing Yang; Li-juan Chen (694-696).
Employing N-benzoyl-salicylhydrazide (H3bzshz) and imidazole (Himdz) as mixed ligands, a novel linear trinuclear Ni(II) complex [Ni3(bzshz)2(Himdz)2(H2O)2]·2DMF (1) has been synthesized and characterized. The three nickel atoms in 1 arrange in a strictly linear structure. The complex exhibits a novel 3D hydrogen bonding framework through the intermolecular O―H···O and N―H···O hydrogen bonding interactions. The magnetic property of 1 has been investigated by variable temperature magnetic susceptibility measurement.The first 3D framework of trinuclear nickel(II) complex based on N-acyl-salicylhydrazide is formed by hydrogen bonding interactions. The magnetic property of the complex has been investigated by variable temperature magnetic susceptibility measurement in the solid state.Display Omitted► Linear trinuclear Nickel(II) complex with mixed ligands of N-acyl-salicylhydrazide ligand and imidazole. ► Hydrogen bonding interactions lead to a novel 3D framework. ► Magnetism study by variable temperature magnetic susceptibility measure.
Keywords: Linear trinuclear Nickel(II) complex; Mixed ligands; Hydrogen bonding; 3D framework; Magnetism;

A new 3D framework constructed from oxo-bridged Keggin chains and metallamacrocyclic polymer chains by Aixiang Tian; Xiaojing Liu; Jun Ying; Dongxia Zhu; Xiuli Wang; Jun Peng (697-701).
A new three-dimensional (3D) framework, [Cu4(btp)4Cu(H2O)2(PW11CuO39)]·2H2O (1) (btp = 1,3-bis(1,2,4-triazol-1-y1)propane), was synthesized under hydrothermal conditions. The 3D framework of compound 1 is constructed by two kinds of chains: inorganic Keggin chain sharing terminal O atoms and tetra-nuclear metallamacrocyclic chain.A new 3D framework was synthesized, exhibiting two kinds of chains: inorganic Keggin chains sharing terminal O atoms and tetra-nuclear metallamacrocyclic chains. These two moieties connect with each other to form a 3D framework.Display Omitted► Two kinds of chains in one compound. ► Oxo-bridged monosubstituted polyoxoanions form an inorganic chain. ► There also exist infinite metallamacrocyclic polymer chain. ► These two moieties form a new 3D framework.
Keywords: Keggin polyoxometalate; Hydrothermal synthesis; Flexible bis(triazole) ligand; Metallamacrocyclic structure;

A unique unit cell containing simultaneous doubly and triply copper(II) complexes bridging by 2,4-pyridine dicarboxylate by Franz A. Mautner; Jörg H. Albering; Montserrat Corbella; Salah S. Massoud (702-705).
The reaction of an aqueous solution containing Cu(ClO4)2, N,N,N′,N″,N″-pentamethylethylene-triamine (pmedien) and 2,4-pyridine dicarboxylic acid disodium salt (Na2.2,4-pydc) afforded {[Cu3(pmedien)3(μ-2,4-pydc)(H2O)2](ClO4)4,[Cu2(pmedien)2(μ-2,4-pydc)(H2O)](ClO4)2}∙4H2O (1). The complex was structurally and magnetically characterized. Single X-ray crystallography for 1 reveals the existence of two independent molecules in the unit cell in which the dinuclear and trinuclear Cu(II) centers are bridging by the 2,4-pyridine dicarboxylato ligands. Magnetic susceptibility measurements of the complex showed that the Cu(II) ions are antiferromagnetically weakly coupled (J  = − 0.27 cm−1).Single X-ray crystallography for {[Cu3(Me5dien)3(μ-2,4-pydc)(H2O)2](ClO4)4,[Cu2(Me5dien)2(μ-2,4-pydc)(H2O)](ClO4)2}∙4H2O (1) reveals the existence of two independent molecules in the unit cell: dinuclear and trinuclear Cu(II) centers bridging by the 2,4-pyridine dicarboxylato ligands. The Cu(II) ions in the complex are antiferromagnetically weakly coupled.Display Omitted► Polynuclear Cu(II) complex containing di- and tri-nuclear entities. ► The Cu(II) centers are bridging by 2,4-pyridine dicarboxylato dianion. ► The complex exhibits very weak antiferromagnetic coupling.
Keywords: Copper; Bridging carboxylate; Polynuclear complexes; Crystal structure; Magnetic properties;

The layered coordination polymer {[Cu(4-bpfp)2(NO3)](NO3)•8H2O} n (1, 4-bpfp = bis(4-pyridylformyl)piperazine) has been prepared by hydrothermal methods and characterized by single-crystal X-ray diffraction. Rare hydrogen-bonded R8 cyclooctane-like octameric water molecule clusters, in an unprecedented twist-chair-chair conformation, are stabilized within the coordination polymer network. Dehydration of 1 results in the crystalline green phase {[Cu(4-bpfp)2(NO3)](NO3)} n 2, which regenerates purple crystalline 1 upon rehydration.The layered coordination polymer {[Cu(4-bpfp)2(NO3)](NO3)•8H2O} n (1, 4-bpfp = bis(4-pyridylformyl)piperazine) possess octameric water molecule clusters, in an unprecedented twist-chair-chair conformation. Dehydration of 1 results in the crystalline green phase {[Cu(4-bpfp)2(NO3)](NO3)} n 2, which regenerates purple crystalline 1 upon rehydration.Display Omitted► Layered copper coordination polymer with bis(4-pyridylformyl)piperazine) (4-bpfp) ligands. ► Unique hydrogen-bonded R8 cyclooctane-like octameric water molecule clusters. ► Crystal-to-crystal transformation with color change on dehydration and rehydration.
Keywords: Coordination polymer; Copper; Crystal structure; Water cluster; Hydrogen bonding;

The luminescent coordination polymer {[Cd2(dms)2(bpmp)1.5]•8H2O} n (1, dms = 2,2-dimethylsuccinate, bpmp = bis(4-pyridylmethyl)piperazine) exhibits [Cd2(dms)2(bpmp)] n layers partially pillared by other crystallographically distinct bpmp ligands into a complex 3-D 3,4,5-connected tetranodal network. Hydrogen-bonded hexadecameric water molecule clusters lie in incipient channels.The luminescent coordination polymer {[Cd2(dms)2(bpmp)1.5]•8H2O} n (1, dms = 2,2-dimethylsuccinate, bpmp = bis(4-pyridylmethyl)piperazine) exhibits [Cd2(dms)2(bpmp)] n layers partially pillared by other bpmp ligands into a complex 3-D 3,4,5-connected tetranodal network. Hydrogen-bonded hexadecameric water molecule clusters lie in incipient channels.Display Omitted► Luminescent cadmium coordination polymer with 2,2-dimethylsuccinate (dms) ligands. ► Partially pillared [Cd2(dms)2(bpmp)] n layers (bpmp = bis(4-pyridylmethyl)piperazine). ► Complex 3-D 3,4,5-connected network topology. ► Hydrogen-bonded hexadecameric water molecule clusters in incipient channels.
Keywords: Coordination polymer; Cadmium; Crystal structure; Water cluster; Hydrogen bonding; Luminescence;

The substituted aniline–phenol ligand binds in the reduced-monoanionic form to the group 4 metals giving fluxional octahedral [{NO}2M(OR)2]-type complexes. The X-ray structures of the Zr- and Hf-complexes revealed cis-N/trans-O binding and an overall C 1 symmetry. All three complexes exhibited high activities in polymerization of L-lactide and rac-lactide. The Zr- and Hf-complexes led to heterotactically enriched PLA.The substituted aniline–phenol ligand forms fluxional octahedral [{ON}2M(OR)2]-type complexes of group 4 metals of cis-N/trans-O binding and overall C 1 symmetry. All three complexes exhibited high activities in polymerization of L-lactide and rac-lactide. The Zr- and Hf-complexes led to heterotactically enriched PLA.Display Omitted► Octahedral group 4 metal complexes of an aniline–phenolate ligand were prepared. ► The complexes were C 1-symmetric in the solid phase and fluxional in solution. ► All complexes are active catalysts in lactide polymerization. ► The PLA obtained by the Zr- and Hf-catalysts is heterotactically enriched.
Keywords: N,O-ligands; Group 4 complexes; Polymerization; Poly(lactic acid);

[Cr(N)(acac)2]: A simple chromium nitride complex and its reactivity towards late transition metals by Erik Donovan Hedegaard; Magnus Schau-Magnussen; Jesper Bendix (719-721).
A new simple chromium(V) nitride complex, Cr(N)(acac)2 (1) has been prepared by nitrogen atom transfer. X-ray crystallography shows a short Cr―N bond at 1.5564(11) Å and equatorial Cr―O distances in the range 1.9387(9)–1.9485(9) Å. 1 reacts as a π-backbonding ligand towards cis-Pt(dmso)Cl2 to form a heterometallic nitride-bridged dimer, [Cl2(dmso)Pt(μ-N)Cr(acac)2(H2O)] (2). 2 has a linear Cr―N―M bridge [172.33(12)°] and a short N―Pt distance at 1.9015(18) Å. Despite a longer Cr―N distance in 2 (1.6228(18) Å), solution EPR reveals a significantly increased 14N hyperfine coupling in 2 as compared to 1.Cr(N)(acac)2 prepared by nitrogen atom transfer exhibits electrophilic reactivity. It reacts as a π-backbonding ligand towards cis-Pt(dmso)Cl2 to form a heterometallic nitride-bridged dimer, which exhibits a strong super hyperfine coupling between the electron spin and the 14N nuclear spin.Display Omitted► Reactivity of Cr(V)nitride complexes. ► Nitride-bridged systems. ► Super hyperfine couplings. ► Multiple bonded systems as backbonding ligands.
Keywords: Nitride; Bridging; Reactivity; Back-bonding; EPR; Platinum;

The layered coordination polymer {[Co3(tBuip)2(HtBuip)2(bpmp)]•bpmp} n (1, tBuip = 5-tert-butylisophthalate, bpmp = bis(4-pyridylmethyl)piperazine) has been prepared by hydrothermal methods and characterized by single-crystal X-ray diffraction. Carboxylate groups of both tBuip and HtBuip ligands construct [Co3(tBuip)2(HtBuip)2] n neutral ribbons with embedded linear {Co3(μ-O)4(μ-OCO)2} trimeric units. Tethering bpmp ligands link the ribbon motifs into [Co3(tBuip)2(HtBuip)2(bpmp)] n grid-like layers. In turn these layers are connected into a supramolecular 3-fold interpenetrated network by hydrogen-bonding mechanisms involving unligated bpmp molecules. Weak ferromagnetic coupling is observed within the trimeric kernels, with some spin canting likely below 3 K.The layered coordination polymer {[Co3(tBuip)2(HtBuip)2(bpmp)]•bpmp} n (1, tBuip = 5-tert-butylisophthalate, bpmp = bis(4-pyridylmethyl)piperazine) contains embedded linear {Co3(μ-O)4(μ-OCO)2} trimeric units that exhibit ferromagnetic coupling, with spin canting likely below 3 K. Unligated bpmp molecules foster a 3-fold interpenetrated primitive cubic supramolecular topology for 1.Display Omitted► Cobalt 5-tert-butylisophthalate coordination polymer has embedded linear trinuclear units. ► Metal carboxylate ribbons link into layers through bis(4-pyridylmethyl) piperazine ligands. ► Three-fold interpenetrated 6-connected supramolecular network. ► Ferromagnetic coupling within {Co3(m-O)4(m-OCO)2} trimeric units.
Keywords: Coordination polymer; Cobalt; Crystal structure; Ferromagnetism;

A new open-framework indium phosphate–phosphite containing intersecting extra-large 16-ring channels by Zhaojun Dong; Yan Yan; Yi Li; Jiyang Li; Jihong Yu; Ruren Xu (727-730).
A new open-framework indium phosphate–phosphite [In9(H2O)6(HPO3)13(H2PO3)2(PO4)(HPO4)][(C6N2H18)3] (InHPO-CJ1) has been hydrothermally synthesized by using 2-methyl-1,5-pentanediamine (MPMD) as the structure-directing agent. It presents a unique pillar-layer framework topology containing three-dimensional intersecting extra-large 16-ring channels. 31P MAS NMR has been studied to confirm the four different coordinations of P atoms in the as-synthesized compound.A new open-framework indium phosphate–phosphite [In9(H2O)6(HPO3)12(H2PO3)3(PO4)2][(C6N2H18)3] has been hydrothermally synthesized, which contains three-dimensional intersecting channel system defined by extra-large 16 rings.Display Omitted► A new open-framework indium phosphate–phosphite has been hydrothermally synthesized. ► It presents a unique pillar-layer framework topology containing intersecting extra-large 16-ring channels. ► 31P MAS NMR has been studied to confirm the four different coordinations of P atoms in the as-synthesized compound.
Keywords: Indium phosphate–phosphite; Extra-large 16-ring channel; NMR; Hydrothermal synthesis;

A new 3D hybrid network based on octamolybdates: The coexistence of common helix and meso-helix by Chun-Jing Zhang; Hai-Jun Pang; Qun Tang; Hui-Yuan Wang; Ya-Guang Chen (731-733).
A new three-dimensional (3D) hybrid compound [Cu2(btb)4][β-Mo8O26] (1), [btb = 1,4-bis(1,2,4-triazol-1-yl)butane], was hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. In compound 1, the copper(II)-btb motif, containing both common helix and meso-helix, displays a 3D 4-net structure with a dia topology, which is further connected by the tetradentate β-[Mo8O26]4− clusters to construct a hybrid network. Additionally, luminescent property of compound 1 is investigated in the solid state at room temperature.A new 3D compound [Cu2(btb)4][β-Mo8O26] (1), [btb = 1,4-bis(1,2,4-triazol-1-yl)butane], was hydrothermally synthesized and characterized, in which, the copper(II)-btb motif with the dia topology, containing both common helix and meso-helix, is further connected by the tetradentate β-[Mo8O26]4− clusters into a hybrid network.Display Omitted► A dia framework formed by the common helix and rare meso-helix. ► β-[Mo8O26]4- anions are exactly trapped in the channels of the open framework. ► The luminescent property of compound 1 has been studied in the solid state.
Keywords: Polyoxometalate; Hydrothermally synthesis; Helix; Luminescence;

Facile routes to manganese(II) triflate complexes by Paul J. Riedel; Navamoney Arulsamy; Mark P. Mehn (734-737).
Manganese(II) chloride reacts with trimethylsilyl triflate (TMS(OTf) where OTf = − OSO2CF3) in a 1:1 mixture of acetonitrile and tetrahydrofuran and after recrystallization affords the linear coordination polymer [MnII(CH3CN)2(OTf)2]n. Each distorted octahedral manganese(II) center in the polymeric chain has trans-acetonitriles and the remaining equatorial coordination positions are occupied by the bridging triflate anions. Dissolving [MnII(CH3CN)2(OTf)2]n in equal volumes of acetonitrile and pyridine followed by recrystallization with diethyl ether yields trans-[MnII(C5H5N)4(OTf)2]. The distorted octahedral geometry of the manganese center features monodentate trans-triflate anions and four equatorial pyridines. Exposure of either [MnII(CH3CN)2(OTf)2]n or [MnII(C5H5N)4(OTf)2] to water readily gives [MnII(H2O)6](OTf)2. XRD reveals hydrogen-bonding interactions between the [MnII(H2O)6]2+ cation and the triflate anion. All three of these species are easily crystallized and provide convenient sources of manganese(II) for further synthetic elaboration.Convenient routes for the preparation of [Mn(CH3CN)2(CF3SO3)2]n, [Mn(C5H5N)4(CF3SO3)2], and [Mn(H2O)6](CF3SO3)2. Each species is readily crystallized and exhibits distinct triflate vibrational features.Display Omitted► Reliable preparative routes for manganese(II) triflates. ► Structures and spectroscopic characterization of these catalyst precursors. ► Caveats regarding susceptibility of the manganese(II) triflates to water.
Keywords: Manganese(II) compounds; Triflate; Crystal structure; Coordination polymer;

Chemical, spectroscopic characterization and antibacterial activities in vitro of a novel gold(I)–ibuprofen complex by Ana Thereza M. Fiori; Wilton R. Lustri; Alviclér Magalhães; Pedro P. Corbi (738-740).
A novel gold(I) complex with ibuprofen was synthesized and characterized by chemical and spectroscopic measurements. Elemental analysis led to the composition AuC14H18O2N. Infrared, 1H and 13C NMR data suggest coordination of the ligand to Au(I) through the oxygen atom of the carboxylic group in a monodentate form. An antibiotic sensitive profile indicated antibacterial activity in vitro of the complex against Gram-negative (E. coli and P. aeruginosa) and Gram-positive (S. aureus) microorganisms. 1H―13C HMBC nuclear magnetic resonance spectrum of the Au(I)–ibuprofen complex.Display Omitted► A novel gold(I) complex with ibuprofen. ► IR and NMR studies permitted proposing oxygen coordination of the COOH group. ► Coordination of CN anion was also confirmed by IR analysis. ► The compound shows biological activities against Gram-negative and positive bacteria.
Keywords: Gold(I); Ibuprofen; NMR; Infrared; Antibacterial assay;

A magnesium–lithium heterometallic coordination network by Paul J. Calderone; Debasis Banerjee; Lauren A. Borkowski; John B. Parise (741-744).
A three-dimensional magnesium–lithium coordination network, Mg2Li(BTC) (HBTC)(DMF)2, (1) (BTC = 1,3,5-benzenetricarboxylate; DMF = N,N-dimethylformamide), the first example of a mixed-metal Mg–Li coordination network, is synthesized using solvothermal techniques. Structural characterization was completed using single crystal x-ray techniques while thermal properties and surface area measurements were conducted by thermogravimetric and BET analysis, respectively.The three-dimensional magnesium–lithium coordination network, Mg2Li(BTC) (HBTC)(DMF)2 is first example of a mixed-metal Mg–Li coordination network and provides an excellent starting point for the targeting of new mixed lightweight metal MOFs.Display Omitted► First example of lightweight heterometallic Li/Mg coordination network. ► Forms 3-D dense network with tetrahedral Li and trigonal bipyramidal Mg centers. ► Loses porosity upon solvent removal.
Keywords: Metal-organic frameworks; Heterometallic coordination polymers; S-block metals; Lightweight metal centers;

A new two-dimensional (2D) polyoxometalate (POM)-based helical coordination polymer, [Cu32-OH)(pdon)3(pca)(H2O)3][SiW12O40]·6H2O (1) (pdon = 1,10-phenanthroline-5,6-dione, Hpca = pyridine-4-carboxlic acid), has been synthesized by in situ generation of pyridine-4-carboxlic acid and 1,10-phenanthroline-5,6-dione from 2-(4-pyridine)imidazo[4,5-f]1,10-phenanthroline under hydrothermal condition, and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction. In complex 1, each [SiW12O40]4− (SiW12) cluster connects with three trinuclear [Cu32-OH)(pdon)3(pca)(H2O)3]4+ metal-organic fragments, meanwhile, each metal-organic fragment also links with three SiW12 polyoxoanions to form two types of one dimensional (1D) helical chains. The adjacent 1D chains with different spiral orientations are connected by the terminal oxygen atom of SiW12 polyoxoanions, leading to the formation of a 2D layer network. Moreover, the photochemical catalysis and electrochemical properties of complex 1 are also reported.A new two-dimensional (2D) polyoxometalate (POM)-based helical coordination polymer, [Cu32-OH)(pdon)3(pca)(H2O)3][SiW12O40]·6H2O (1) (pdon = 1,10-phenanthroline-5,6-dione, Hpca = pyridine-4-carboxlic acid), has been synthesized by in situ generation of pyridine-4-carboxlic acid and 1,10-phenanthroline-5,6-dione from 2-(4-pyridine)imidazo[4,5-f]1,10-phenanthroline under hydrothermal conditions.Display Omitted► 1 is the first example of imidazole cycle oxidation to –COO− in POM-based complex. ► Complex 1 is a 2D helical network based on POM by in situ ligand transformation. ► Complex 1 exhibits good photocatalytic and electrocatalytic activity.
Keywords: Polyoxometalate; Helical; In situ ligand transformation; Coordination polymer; Crystal structure;

Zinc(II) and cadmium(II) complexes based on 2-(3,5-dimethyl-1H-pyrazol-1-yl)-6-(4-methoxyphenyl)pyrimidine-4-carboxylic acid: Synthesis, structure and luminescence by Mark B. Bushuev; Viktor P. Krivopalov; Elena B. Nikolaenkova; Natalia V. Pervukhina; Dmitrii Yu. Naumov; Marianna I. Rakhmanova (749-752).
Zinc(II) and cadmium(II) complexes, ZnL2  ⋅ 0.5H2O, ZnL2  ⋅ 2MeOH and CdL2  ⋅ 1.5H2O, based on a new hybrid compound, 2-(3,5-dimethyl-1 H-pyrazol-1-yl)-6-(4-methoxyphenyl)pyrimidine-4-carboxylic acid (HL), have been synthesized. They are the first examples of metal complexes with pyrazolylpyrimidinecarboxylates. The complex ZnL2  ⋅ 2MeOH was structurally characterized. It has mononuclear structure; zinc atom is in the distorted octahedral coordination polyhedron 4N + 2O formed by donor atoms of two coordinated L ions. The compounds HL, ZnL2  ⋅ 0.5H2O and CdL2  ⋅ 1.5H2O manifest bright blue photoluminescence.Graphical Abstract — SynopsisZinc(II) and cadmium(II) complexes, ZnL2  ⋅ 0.5H2O, ZnL2  ⋅ 2MeOH and CdL2  ⋅ 1.5H2O (HL = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-6-(4-methoxyphenyl)pyrimidine-4-carboxylic acid), have been synthesized. They are the first examples of metal complexes based on pyrazolylpyrimidinecarboxylic acids. The complex ZnL2  ⋅ 2MeOH has mononuclear structure; zinc atom is in the distorted octahedral coordination polyhedron 4 N + 2O formed by donor atoms of two coordinated L ions. The compounds HL, ZnL2  ⋅ 0.5H2O and CdL2  ⋅ 1.5H2O manifest bright blue photoluminescence.Display Omitted►Zinc(II) and cadmium(II) complexes with pyrazolylpyrimidinecarboxylate. ►Pyrazolylpyrimidinecarboxylate acts as a chelating tridentate ligand. ►Compounds manifest bright blue photoluminescence.
Keywords: Pyrazole; Pyrimidine; Carboxylate; Zinc(II); Cadmium(II); Luminescence;

A new ligand, bispyridin-2-ylmethyl-thiophen-2-ylmethylamine, 2ThDPA (1), was synthesized and its complexes of Cu(II) were isolated. When Cu(NO3)2 was used as the metal source, a mononuclear complex with the formula [Cu(1)(NO3)2], 2, was isolated featuring both nitro groups coordinated bidentate to the Cu. 2 crystallizes in the monoclinic P21/c space group with a = 14.848, b = 8.212, c = 32.752 Å, β = 102.52° and V = 3898.3 Å3. When CuSO4 was used as the metal source, a homobinuclear sulfato-bridged complex was isolated with the formula [Cu(1)SO4]2·CH3CN, 3. 3 crystallizes in the monoclinic P21/n space group with a = 10.457, b = 17.035, c = 12.425 Å, β = 108.72° and V = 2096.17 Å3. The structures of 2 and 3 are shown to be stabilized by an extended system of π–π stacking and hydrogen-bonding interactions. Comparison of the electronic absorption spectra of the ligand and complexes shows that complexation is maintained in solution and that the ligand absorption is attenuated in the complexes, depending on the counter-anion utilized.Copper(II) complexes with a new thiophen-2-yl derivatized dpa ligand and nitrato and sulfato anions were prepared and characterized displaying unique bridging-bidentate coordination by the sulfato anions and anion dependent electronic spectra.Display Omitted► New tripodal N3S-type dipicolylamine-based ligand with a thiophene ring pendant. ► Cu(II) complexes display structure dependent on the counter-anion. ► Mononuclear nitrato complex, rare bridging bidentate sulfato homobinuclear complex. ► Quenching of the ligand's π–π* absorption band is dependent on the counter-anion.
Keywords: Copper(II); N3S-type ligands; Bridging-bidentate sulfate;

Mononuclear complex bis(aspirinato) bis(2-methylimidazole) copper(II), Cu(asp)2 (2-MeIm)2 (1), has been synthesized and spectroscopically characterized. The biomimetic catalytic activities of this complex and our previously characterized complexes, Cu(asp)2 (1,2-MeIm)2 (2), Cu(Hsal)2 (1,2-MeIm)2 (3), and Cu(sal)(2-MeIm)3, (4) [H2sal = salicylic acid and MeIm = methylimidazole], for the oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone and the oxidative dealkylation of 2,4,6-tri-tert-butylphenol to 2,6-di-tert-butyl-1,4-benzoquinone and 4,6-di-tert-butyl-1,2-benzoquinone as the main products are reported. Complexes 1 and 2 are found to be potent SOD mimics and their SOD activities are compared with those obtained previously for complexes 3 and 4.Mononuclear copper(II) aspirinate or salicylate complexes with methylimidazole ligands were found to catalyze the oxidation of 3,5-di-tert-butylphenol to corresponding o-quinone and the oxidative dealkylation of 2,4,6-tri-tert-butylphenol (TTBP) to o-DTBQ and p-DTBQ. The complexes are potent SOD mimics.Display Omitted► Mononuclear bis(aspirinato) bis (2-methylimidazole) copper(II) has been synthesized and characterized. ► Mononuclear copper(II) aspirinate and salicylate complexes with methylimidazole ligands are used to catalyze the oxidation of DTBC and oxygenation of TTBP. ► The complexes are potent SOD mimics.
Keywords: Mononuclear copper(II) aspirinate; Catecholase; Oxidative dealkylation of phenol; SOD mimics;

Synthesis, characterization of hetero-bimetallic complex and application in the polymerization of ε-caprolactone by Xiaobo Pan; Ai Liu; Lihui Yao; Lei Wang; Jinfeng Zhang; Jincai Wu; Xuebo Zhao; Chu-Chieh Lin (763-766).
The reaction of 2,2′-ethylidenebis(4,6-di-tert-butylphenol)(EDBP-H2) with sodium, Al(Me)3 and BnOH with a molar of ratio of 1:1:1:1 in THF gives hetero-bimetallic complex of [(EDBP)Al(CH3)(μ2-OBn)Na(THF)3](1) in 85% yield. In order to investigate the different anion effects on the ROP of ε-caprolactone, complexes [(EDBP)2Al][(Li)(THF)2] (2) and [(EDBP)2Al][(Na)(THF)2] (3) were prepared in an analogous manner to that of 1 in 63% and 71% yields respectively. Experimental results show that hetero-bimetallic complex 1 is an efficient catalyst for the ring-opening polymerization of ε-caprolactone.The reaction of 2,2′-ethylidenebis(4,6-di-tert-butylphenol)(EDBP-H2) with Na, Al(Me)3 and BnOH with a molar of ratio of 1:1:1:1 in THF gives complex of [(EDBP)Al(CH3)(μ2-OBn)Na(THF)3](1). Experimental results show that complex 1 is an efficient catalyst for the ring-opening polymerization of ε-caprolactone.Display Omitted►Hetero-bimetallic complexes of 1-4 were prepared in an analogous manner. ►Fine crystals 1, 2 and 4 were obtained by crystallization from THF/hexane. ►Hetero-bimetallic complexes of 1–4 were used as catalyst and application in the polymerization of ε-caprolactone. ►Complex 1 is an efficient catalyst for the ROP of ε-caprolactone.
Keywords: Hetero-bimetallic complex; ε-Caprolactone; Catalyst; Ring-opening polymerization;

A novel transition metal substituted tungstoarsenate [Cu2(phen)2(μ-ox)]{[Cu(phen)(H2O)2][Cu4 (H2O)4Cu2(phen)2(AsW9O33)2]}·6H2O (ox = oxalate, phen = 1,10-phenanthroline) (1) has been synthesized by reaction of K14[As2W19O67(H2O)]·nH2O, CuCl2·2H2O, H2C2O4·2H2O and phen under hydrothermal conditions and characterized by elemental analyses, IR and UV spectra and X-ray single-crystal diffraction. 1 displays a 1D chain architecture constructed by alternating hexa-Cu sandwiched units {[Cu(phen)(H2O)2]2[Cu4(H2O)4Cu2(phen)2(AsW9O33)2]}2− and dinuclear copper(II)-oxalate complexes [Cu2(phen)2(μ-ox)]2+. The 3D supramolecular network can be established by intra- and inter-molecular ππ packing interactions. To the best of our knowledge, 1 represents the first 1D chain-like inorganic–organic hybrid tungstoarsenate with mixed organic ligands containing hexa-nuclear sandwiched units bridged by copper-oxalate complex linkers.The first example of 1D chain-like inorganicorganic hybrid tungstoarsenate with mixed organic ligands containing hexa-nuclear sandwiched units bridged by copper-oxalate complex linkers has been prepared.Display Omitted► A novel TMC-substituted tungstoarsenate displays 1D chain architecture. ► Hexa-Cu sandwich-type polyanions and di-Cu complexe cations alternating connected. ► The first 1D chain-like hybrid tungstoarsenate with mixed organic ligands. ► ππ interactions between the neighboring phen ligands leading to the 3D framework.
Keywords: Polyoxometalate; Tungstoarsenate; Hybrid material; Oxalate; Sandwich-type structure;

Unprecedented (3,4)-connected self-catenated network based on V-shaped building blocks by Jun Zhao; Dong-Sheng Li; Zong-Zhi Hu; Wen-Wen Dong; Kun Zou; Jack Y. Lu (771-774).
An unprecedented 2D coordination polymer with unique (3,4)-connected self-catenated topology, arising from the parallel interlocking of 1D loop chains via shared binuclear subunits, were prepared from CdII, 5-nitroisophthalic acid and 4,4′-dipyridylamine. The thermal stability and photoluminescence property as well as the photocatalytic performance of 1 were also examined, and the results indicated that 1 shows photocatalytic activity for dye degradation under UV light.The incorporation of 5-nitroisophthalate and 4,4′-dipyridylamine as bridging tectons to bind Cd(II) leads to an unprecedented 2D (3,4)-connected self-catenated motif.Display Omitted► V-shaped Co-ligand system. ► Novel (3, 4)-connected self-catenated network with (4.62)2(42.62.82) topology. ► This CdII-compound shows photocatalytic activity for dye degradation under UV light.
Keywords: Coordination polymer; Cadmium (II); Photoluminescence; Photocatalytic activity;

A novel organically templated aluminoborate, AlB3O6(OH)·0.5(C2H10N2) 1 was synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. Its aluminoborate architecture features the alternative connection of AlO3(OH) tetrahedra and B3O6 polyanions, giving rise to a sheet with hnb topology. Two adjacent antiparallel sheets sandwich H2en templates by hydrogen bonding interactions to produce a slab block (en = ethylenediamine). These slab blocks are stacked in a −AAAA-sequence and further cohered entirely by relatively weak van der Waals interactions to form its entire structure. Further characterizations for 1 are accomplished by IR, element analysis, and thermal analysis.A new organically templated aluminoborate AlB3O6(OH)·0.5(C2H10N2) was hydrothermally synthesized. Its structure is built by the alternate connection of the B3O6 polyanions and AlO3(OH) units to form hnb-layer topology with diprotonated ethylenediamine templates occupying alternatively half of the interlayers.Display Omitted► The first combination of AlO4 and B3O6 units produces a layered aluminoborate. ► The inorganic layer has hnb topology containing uncommon old 9-membered rings. ► The organic templates occupy alternatively half of the interlayers.
Keywords: Aluminoborate; Hydrothermal synthesis; Organic template; Layered structure;

1D ferromagnetic Dy(III) compound showing supramolecular four-connecting rod-packing architecture by Yi-dong Luo; Gong-ming Sun; De-ming Li; Feng Luo (778-780).
A new Dy(III) compound, namely Dy(4-nitrobenzoato)3(H2O) (1) featuring a 1D chain-like structure, was obtained by hydrothermal self-assembly of Dy(ClO4)3 and 4-nitrobenzic acid. The magnetic studies suggest weak intrachain ferromagnetic interactions and the magnetic data were interpreted by means of non-critical scaling theory with the parameters of C 1  = 13.79 cm3mol−1K, E 1  = 0.26 K, C 2  = 0.58 cm3mol− 1K, E 2  = − 34.86 K.A new Dy(III) compound, namely Dy(4-nitrobenzoato)3(H2O) (1) featuring a 1D chain-like structure, was obtained by hydrothermal self-assembly of Dy(ClO4)3 and 4-nitrobenzic acid. The magnetic studies suggest weak intrachain ferromagnetic interactions and the magnetic data were interpreted by means of non-critical scaling theory with the parameters of C 1  = 13.79 cm3mol− 1K, E 1  = 0.26 K, C 2  = 0.58 cm3mol− 1K, E 2  = − 34.86 K.Display Omitted► We demonstrated an effective approach to access of 1D Dy(III) compounds. ► The magnetic studies suggest weak intrachain ferromagnetic interactions and were interpreted by means of non-critical scaling theory. ► The Dy(III) ions shows the D4d square-antiprism geometry, suggesting the potential possibility of single-ion magnets or SCM.
Keywords: Hydrothermal synthesis; Dy(III) compound; Ferromagnetic interaction;

Tripodal ligand NTB (N-substituted tris(benzimidazol-2-ylmethyl)amine) was functionalized with 3-(animopropyl) triethoxysilane (APTEOS) to give a new bifunctional ligand Si-CNTB. The coordination of N atoms on Si-CNTB with Ln(III) ions afforded efficient luminescent centers and the co-hydrolyzation of silane groups with TEOS (tetraethoxysilane) produced covalently linked hybrid particles in sub-micron scale. Visible to near infrared photoluminescence and N2 adsorption properties were observed in this new type of inorganic–organic hybrid materials.Ce/Tb/Yb/Er(III) sub-micron hybrid particles were obtained by the covalently linking of a modified NTB ligand with long-chain silicon ester groups to the in-situ generated Si―C and Si―O―Si host. The obtained materials show both sensitized luminescence of lanthanide ions and gas adsorption behavior.Display Omitted► A novel series of covalently linking Ln(III) hybrid materials are synthesized. ► The hybrid materials show special sensitized luminescence of Ln(III) ions. ► The hybrids also show efficient gas adsorption behavior.
Keywords: Covalently linked hybrid material; Ln(III); Photoluminescence; Gas adsorption;

A 1D copper(II) chain with novel hexanuclear copper(II) units [Cu6(L)2(py)4] (H6L =  N,N′-(2,6-pyridine-dicarboxyl)-disalicylhydrazide, py = pyridine) as secondary building blocks, was synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis. The hexanuclear unit is formed by the assembly of two tetranuclear subunits via two public copper ions coordinating simultaneously to two L6− ligands, and the 1D chain structure of the compound is constructed by the connection of the hexanuclear units via the bridging of the phenolic oxygen atoms of the L6− ligands. The magnetic study of the compound indicates an antiferromagnetic coupling interaction between Cu(II) ions.The title one-dimensional copper(II) chain features novel hexanuclear secondary building blocks [Cu6(L)2(py)4] (H6L =  N,N′-(2,6-pyridine-dicarboxyl)-disalicylhydrazide) and displays an antiferromagnetic coupling interaction between Cu(II) ions.Display Omitted► A 1D chain featuring hexanuclear units was obtained from a multi-salicylhydrazide ligand. ► H6L is the first ligand with multi-carboxyl and multi-salicylhydrazide groups. ► It is the highest-nuclear unit of polymer connected by N-acyl-salicylhydrazide itself. ► The title compound presents an antiferromagnetic coupling interaction.
Keywords: Coordination polymer; Copper; Salicylhydrazide; Crystal structure; Magnetic property;

Design and construction of self-penetrating coordination frameworks by Xi-Jun Ke; Dong-Sheng Li; Miao Du (788-803).
Self-penetrating coordination networks have recently been demonstrated as an important family of coordination polymers with new topologies and properties. However, the design and control of self-penetrating systems is still an enthralling challenge. In this review, we present the topological types of self-penetrating coordination networks, mainly with single-connectivity, and summarize their designing and constructing strategy.This review discusses the recent development on the design and construction of self-penetrating coordination nets showing various topological types, mainly with single-fold connectivity.Display Omitted►The topological types of self-penetrating coordination networks have been summarized. ►The general tactics for their rational design have been proposed. ►In such area, the next phase of growth has been shown.
Keywords: Self-penetrating nets; Single-fold connectivity; Coordination frameworks; Topologies;