Inorganic Chemistry Communications (v.28, #C)

Contents List (iii-viii).

Three 3d–4f heterometallic coordination polymers based on polydentate ligand and sulfate: Synthesis, crystal structure and photoluminescent properties by Ya-guang Sun; Shu-ju Wang; Ke-long Li; En-Jun Gao; Gang Xiong; Mei-yan Guo; Zhen-he Xu; Yan-Wen Tian (1-6).
Three heterometallic coordination polymers [Gd2Cu(Hbidc)2(SO4)2(H2O)7]n (1), [Eu2Cu(Hbidc)2(SO4)2(H2O)7]n (2), and [Dy2Cu(Hbidc)2(SO4)2(H2O)7]n (3) (H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions. They are characterized by elemental analysis (EA), infrared (IR) spectroscopy, thermogravimetric analysis (TGA), single crystal X-ray diffraction, and power X-ray diffraction (XRD). The results reveal that all complexes present almost identical three-dimensional (3D) PtS topology framework structures. The photoluminescent properties of 2 and 3 are investigated.Three heterometallic coordination polymers ([Gd2Cu(Hbidc)2(SO4)2(H2O)7]n (1), [Eu2Cu(Hbidc)2(SO4)2(H2O)7]n (2), [Dy2Cu(Hbidc)2(SO4)2(H2O)7]n (3)) present almost identical three-dimensional (3D) PtS topology framework structures.Display Omitted► Three novel 3d–4f coordination polymers have been synthesized. ► Compouds 13 all show 3D frameworks with (4,4) — connected PtS-type Topology. ► The luminescent properties of 2 and 3 reveal 4f-metal-centered emissions.
Keywords: Hereometallic coordination polymers; Crystal structure; Fluorescence;

An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by elemental analyses, IR, UV and CD spectrum, powder X-ray diffraction, TG-DTA and single-crystal X-ray diffraction. The asymmetric unit of 1 consists of a monocapped trivacant Keggin [AsIIIAsVMo9O34]6 − subunit, a pendant [Cu(en)2(H2O)]2 + cation, a pendant [Cu(en)(H2O)]2 + cation, one bridging [Cu(en)2]2 + cation and two lattice water molecules. It should be noted that 1 illustrates a one-dimensional (1D) helical chain assembled by {[Cu(en)(H2O)][(Cu(en)2(H2O)][AsIIIAsVMo9O34)]}2 − clusters and [Cu(en)2]2 + linkers.A new organic–inorganic hybrid arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O has been hydrothermally synthesized, which displays a 1D helical chain assembled from {[Cu(en)(H2O)][(Cu(en)2(H2O)][AsIIIAsVMo9O34)]}2 − clusters and [Cu(en)2]2 + linkers.Display Omitted► Reports on TM-containing lacunary arsenomolybdate fragments are rather rare. ► A novel organic–inorganic arsenomolybdate hybrid was hydrothermally obtained. ► The first hybrid assembled from [AsIIIAsVMo9O34)]} clusters and {Cu(en)2} linkers ► The hybrid displays a unique 1D helical chain.
Keywords: Arsenomolybdate; Polyoxometalate; Helical chain; Circular dichroism spectrum;

A novel 1D linear Zn(II) coordination polymer {[Zn(BPDC)(H2O)3] · 3H2O}n (BPDC2 −: 2,2′-bipyridine-4,4′-dicarboxylate) was obtained by hydrothermal methods. In this complex, an unusual coordination mode, which BPDC2 − ligand adopts two N atoms and only one O atom to bridge Zn(II) ions into a rigid liner chain, is observed. The 1D chain further assembles into a 3D supramolecular architecture through hydrogen bonds and π–π interactions among chains. In addition, the complex exhibits a strong fluorescence at 381 nm in the solid state, indicating that it may be a candidate for near ultraviolet luminescent material.A novel 1D linear Zn(II) coordination polymer {[Zn(BPDC)(H2O)3]3H2O}n (BPDC2 −: 2,2′-bipyridine-4,4′-dicarboxylate) was synthesized hydrothermally, in which BPDC2 − adopts two N atoms and only one O atom to bridge Zn(II) ions into a rigid liner chain. The complex exhibits a strong fluorescence at 381 nm in the solid state.Display Omitted► A novel 1D linear Zn(II) coordination polymer was synthesized hydrothermally. ► The ligand adopts an unusual tridentate coordination mode. ► The complex exhibits a strong near ultraviolet fluorescence in the solid state.
Keywords: Zinc(II) coordination polymer; 2,2′-bipyridine-4,4′-dicarboxylic acid; Crystal structure; Photoluminescence;

An anionic metal–organic framework based on infinite [In3(μ 3-OH)2] n inorganic chains synthesized in ionic liquid by Wen-Juan Ji; Quan-Guo Zhai; Shu-Ni Li; Yu-Cheng Jiang; Man-Cheng Hu (16-19).
A 3D metal–organic framework, namely, {[EMIM][In3(μ 3-OH)2(1,2,4,5-BTC)2∙2H2O]} n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), was synthesized by using 1-ethyl-3- methylimidazolium bromide ([EMIM]Br) ionic liquid as solvent. The 7-coordinated pentagonal bipyramidal In(1) and octahedral In(2) atoms are connected by the μ 3-OH groups to form an infinite [In3(μ 3-OH)2] n inorganic chain along the a-axis, which are further extended by 1,2,4,5-BTC ligands to generate the 3D anionic microporous framework of 1. The [EMIM]+ cations occupy the 1D channels acting as template and charge-balancing species. Compound 1 shows strong blue luminescence and remarkable photocatalytic degradation of methylthionine chloride.An anionic porous indium MOF constrcuted from [In33-OH)2] n inorganic chains exhibiting blue luminescence and remarkable photocatalytic activity.Display Omitted► Ionothermal synthesis ► Anionic In-MOFs based on [In33-OH)2] n inorganic chain ► Rod-packing topological net ► Blue photoluminescence and remarkable photocatalytic activity
Keywords: Metal–organic frameworks; Ionic liquid; Indium; 1,2,4,5-Benzenetetracarboxylate;

Syntheses and characterizations of two-dimensional lanthanide coordination polymers based on anthraquinone-1,4,5,8-tetracarboxylic acid by Wei-Hong Yan; Song-Song Bao; Liu-liu Ding; Chang-Sheng Lu; Qing-Jin Meng; Li-Min Zheng (20-24).
A series of isostructural two-dimensional lanthanide complexes with the formula [Ln(Haqtc)(H2O)4·xH2O]n (Ln = Nd, 1; Sm, 2; Eu, 3; Tb, 4; Dy, 5; Er, 6.) were synthesized by treating H4aqtc (H4aqtc = anthraquinone-1,4,5,8-tetracarboxylic acid) with lanthanide(III) salts under hydrothermal conditions. 3-D structures are formed by inter-layer hydrogen bonds. Magnetic susceptibility measurements of complexes 4 and 5 in temperature range 2–300 K were performed, which showed dominant weak ferromagnetic interactions in 4 and slow magnetization relaxation in 5.Six isostructural lanthanide complexes, based on anthraquinone-1,4,5,8-tetracarboxylic acid (H4aqtc), showed layer-like structures and 3-D frameworks formed by interlayer hydrogen bonds. The magnetic properties of complexes 4 and 5 were investigated.Display Omitted► Six isostructural lanthanide complexes were synthesized and characterized. ► 3-D structures are formed by inter-layer hydrogen bonds. ► Magnetic properties results showed slow magnetization relaxation in complex 5.
Keywords: Lanthanide; Coordination polymer; Anthraquinone-1,4,5,8-tetracarboxylic acid; Hydrogen bond;

A 3D multifunctional lanthanide metal-organic framework (MOF), Er4(TCPS)3(H2O)6·10DMF·4H2O (JUC-99) (H4TCPS = tetrakis(4-carboxyphenyl)silane, DMF =  N,N′-dimethylformamide and JUC = Jilin University China) has been synthesized by self-assembly of Er(III) ions and rigid silicon-centered tetrahedral carboxylate ligands under solvothermal reactions. X-ray crystallography reveals that JUC-99 exhibits a unique trinodal (4,12)-connected topology, constructed from tetranuclear erbium clusters as 12-connected nodes and tetrahedral ligands TCPS as 4-connected nodes. To the best of our knowledge, JUC-99 is the first example of lanthanide MOFs with trinodal (4,12)-connected topology structure. In addition, the luminescent and magnetic properties of the compound are investigated.A 3D multifunctional lanthanide MOF, Er4(TCPS)3(H2O)6·10DMF·4H2O (JUC-99) has been synthesized by self-assembly of Er(III) ions and rigid silicon-centered tetrahedral carboxylate ligands under solvothermal reactions. X-ray crystallography reveals that JUC-99 exhibits a unique trinodal (4,12)-connected topology. In addition, the luminescent and magnetic properties of the compound are investigated.Display Omitted► Synthesis of the first rare earth MOF with trinodal (4,12)-connected topology. ► The 3D framework was proved by single-crystal X-ray diffraction. ► The luminescent and magnetic properties were investigated.
Keywords: Metal-organic frameworks; Tetrakis(4-carboxyphenyl)silane; (4,12)-Connected topology; Magnetic property; Fluorescence;

A colorimetric phosphorescent iridium(III) complex chemodosimeter (Ir1) for Hg2 + has been prepared and confirmed by NMR, MS, and crystal data, which displays a high selectivity and antidisturbance for Hg2 + detection among relevant metal ions. Phosphorescent studies show that the luminescence intensity at 598 nm decreased to ca. 12%, while the luminescence intensity in 441 nm increased to ca. 195%. The ratio of Ir1 responding to Hg2 + was determined to be 1:1 by UV–vis absorption and phosphorescent emission measurements. Further study demonstrates that the detection limit on phosphorescent response of the sensor to Hg2 + is down to 10− 6  M range. The mechanism study shows that the interaction between the S atom of ancillary ligand and Hg2 + is responsible for the highly selective and sensitive phosphorescent senor for Hg2 +.A colorimetric phosphorescent iridium(III) complex chemodosimeter (Ir1) for Hg2 + has been prepared. The luminescence intensity in 598 nm decreased to ca. 12%, while the intensity in 441 nm increased to ca. 195%. The ratio of Ir1 responding to Hg2 + was determined to be 1:1.Display Omitted► This complex can serve as a chemodosimeter for Hg2 + with naked-eye detection. ► New chemodosimeter have a highly selective Uv-vis and PL response for 2 +. ► New chemodosimeter has a 1:1 interaction with Hg2 +.
Keywords: Cyclometalated iridium(III) complex; Bis(diphenylthiophosphoryl)amide; Chemodosimeter; Mercury(II);

Various β-aminoalcohols were prepared by the ring opening reaction of epoxides with aromatic amines in the presence of Fe(III) substituted Wells–Dawson type polyoxometalate, α2-[(n-C4H9)4N]7P2W17FeO61·3H2O, as an efficient catalyst. The reaction was performed under neutral condition at room temperature and afforded the corresponding products in high to excellent yields.Fe(III) substituted Wells–Dawson type polyoxometalate, α2-[(n-C4H9)4N]7P2W17FeO61·3H2O, can act as a mild, efficient, and convenient catalyst for the ring opening of epoxides with aromatic amines at room temperature in acetonitrile.Display Omitted► The use of α2-[(n-C4H9)4N]7P2W17FeO61·3H2O as catalyst. ► Aminolysis of epoxides by α2-[(n-C4H9)4N]7P2W17FeO61·3H2O ► Catalytic ring-opening of epoxides with aromatic amines ► High to excellent yields for giving the 1,2-aminoalcohols
Keywords: Catalysis; Ring opening; Epoxides; Aromatic amines; Aminolysis;

Four new metal–organic coordination polymers, [Cd2(sbpdc)2(bpy)] (1), [Cd(sbpdc)(bpp) 1/2 ] (2), [Co(sbpdc)(bpy)] (3) and [Co(sbpdc)(bpp)(H2O)] (4) (H2sbpdc = sulfone-4,4′-biphenyldicarboxylic acid, bpy = 4,4′-bipyridine, bpp = 1,3-bis(4-pyridyl)propane) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectra. Compound 1 displays a 3D 6-connected twofold interpenetrated net with pcu topology, while 2 contains 1D infinite Cd-O-Cd chains. Compound 3 is a new 3D binodal network with the point symbol of (63) (67  ⋅ 83), whereas compound 4 has a 1D double chain. Moreover, the PXRD, TGA, luminescent and magnetic property were also investigated.We have successfully synthesized four new coordination polymers under solvothermal conditions. They have intriguing structures and topologies. The different coordination modes of the carboxylate ligand have a significant effect on the structures.Display Omitted► Four new coordination polymers were prepared by hydrothermal method. ► The coordination modes of the ligand have effect on the structures. ► Both of two cadmium coordination polymers emit intense fluorescence. ► Compound 3 reveals antiferromagnetic exchange interactions.
Keywords: Coordination polymers; Coordination mode; Magnetic property; 3D framework; Fluorescence;

The self-assembly of pyridinecarboxylate ligand (H2L) with mixed metal ions under hydrothermal conditions afforded a new heterometallic coordination polymer, [DyAg(L)2(H2O)]n·2n(H2O) (1 H2L = 5-(pyridine-4-ylmethoxy)-isophthalic acid). Single-crystal X-ray diffraction analysis reveals that 1 features an unusual three-dimensional (3D) pillar-layer framework with an unprecedented (3,4,5)-connected topology. Interestingly, each individual structure is interpenetrated by another identical one.Presented here is a new heterometallic coordination polymer, [DyAg(L)2(H2O)]n·2n(H2O) (1 H2L = 5-(pyridine-4-ylmethoxy)-isophthalic acid), which features an unusual 3D pillar-layer framework with an unprecedented (3,4,5)-connected topology.Display Omitted► New heterometallic coordination polymer based on T-shaped pyridinecarboxylate ligand. ► It features an unusual 3D pillar-layer framework. ► It presents an unprecedented (3,4,5)-connected topology.
Keywords: Pyridinecarboxylate; Hydrothermal synthesis; Pillar-layered framework; Topology;

Organic sulfide oxygenation by hydrogen peroxide (H2O2) was effectively accomplished by using iron(III) chloride or iron(III) bromide as the catalyst. The distribution of products between sulfoxide and sulfone is strongly solvent-dependent, and a 100% selectivity for sulfoxide was achieved with FeCl3 in a 1:1 methanol/water mixture.Fe(III) halides catalyze H2O2 oxygenation of sulfides to sulfoxide and sulfone in general, and selectively to the former in 1:1 methanol–water mixture.Display Omitted► Ability of FeX3 to catalyze the H2O2 oxygenation of organic sulfides ► Solvent dependence of product distribution ► 100% selectivity for sulfoxide using MeOH:H2O mixture solvent
Keywords: Catalytic oxygenation; Organic sulfide; Fe(III) halides; Hydrogen peroxide;

A new polymorph telluridoindate [In(en)3][In5Te9(en)2] with photocatalytic properties by Rong Chen; Jian Zhou; Xing Liu; Feilong Hu; Litao An; Yuhe Kan; Chen-jian Xue (55-59).
A new polymorph telluridoindate [In(en)3][In5Te9(en)2] (denoted as β-type, en = ethylenediamine) has been solvothermally synthesized and characterized. The crystal data for the β-type are listed as follows: monoclinic, space group Cc (No. 9), a  = 11.642(2), b  = 20.421(4), c  = 17.577(4) Å, β  = 92.20(3)°, V  = 4175.7(14) Å3, Z = 4. The β-type contains organic-decorated [In4Te9(en)]6 − supertetrahedral cluster and [InTe3(en)]3 − tetrahedron, which are interconnected to form an organic-decorated 2-D telluridoindate layer of [In5Te9(en)2 3 −]n with 9-membered rings. Two relevant conformers of telluridoindates are compared with each other. The β-type indicates absorption edge at 2.23 eV and exhibits photocatalytic activity for degradation of methyl orange (MO).A new polymorph telluridoindate [In(en)3][In5Te9(en)2] (denoted as β-type, en = ethylenediamine), based on [In4Te9(en)]6 − supertetrahedral cluster unit, has been solvothermally synthesized. 1 exhibits photocatalytic activity for degradation of methyl orange (MO).Display Omitted► A new polymorph telluridoindate (β-type) has been solvothermally synthesized. ► Inorganic polymorphisms are relatively rare. ► The β-type displays exhibits semiconducting and photocatalytic properties.
Keywords: Solvothermal synthesis; Polymorph; Telluridoindate; Photocatalytic properties; Crystal structure;

Synthesis and cytotoxicity of a ruthenium nitrosyl nitric oxide donor with isonicotinic acid and a cell penetrating peptide by Leonardo Elias Figueiredo; Eduardo Maffud Cilli; Roberto Augusto Silva Molina; Enilza Maria Espreafico; Elia Tfouni (60-63).
The syntheses and properties of trans-[Ru(NH3)4(L)(NO)](BF4)3 (L = isonicotinic acid (inaH) (I) or ina-Tat48–60 (II)) are described. Tat48–60, a cell penetrating peptide fragment of the Tat regulatory protein of the HIV virus, was linked to the ruthenium nitrosyl through inaH. I and II release NO after reduction forming trans-[Ru(NH3)4(L)(H2O)]3 +. The IC50 values against B16-F10 melanoma cells of I and II (21 μmol L− 1 and 23 μmol L− 1, respectively) are close to that of the commercially available cisplatin (33 μmol L− 1) and smaller than similar complexes. The cytotoxicity is assigned to the NO released from I and II.Tat48–60 (GRKKRRQRRRPPQ) is a cell penetrating fragment of the HIV virus Tat protein. The cytotoxicity of the complex against B16-F10 melanoma cells is similar to that of cisplatin.Display Omitted► The Tat48-60 cell penetrating peptide was linked to a ruthenium nitrosyl. ► Nytrosil complexes with isonicotinic acid or peptide release NO after reduction. ► The complexes are as toxic as cisplatin against B16F10 melanoma cells. ► The complexes induce 51% (I) and 38% (II) apoptosis at 1 × 10− 4  mol L-1 concentration. ► The cytotoxicities, assigned to NO release, are higher than similar nytrosils.
Keywords: Ruthenium; Nitric oxide; Cell penetrating peptide; Tat48–60; B16-F10 melanoma cells; Cytotoxicity;

Short metal–metal separations and in vitro anticancer studies of a new dinuclear silver(I)-N-heterocyclic carbene complex of para-xylyl-linked bis-benzimidazolium salt by Muhammad Adnan Iqbal; Rosenani A. Haque; Srinivasa Budagumpi; Mohamed B. Khadeer Ahamed; Amin M.S. Abdul Majid (64-69).
A new benzyl-substituted bis-benzimidazolium derivative featuring a para-xylene spacer (1) has been prepared. Reaction of 1 with Ag2O in stoichiometric ratio followed by metathesis with KPF6 yielded a dinuclear silver-carbene complex 2. The benzimidazolium ligands in 2 are arranged in a head-to-head fashion (2:2), spanning a short Ag―Ag separation of 3.10(6) Å between two complex units with the other Ag center of each unit remaining uninteracted. Molecular structure of complex 2 is elucidated by single crystal X-ray diffraction method. Both, 1 and 2, were tested for their potential antiproliferative activity against human colorectal carcinoma (HCT 116) and human leukemia (HL 60) cell lines. Almost similar effects were found for both the cell lines; however, complex 2 displayed more specificity and nearly six fold higher anticancer activity compared to 1 toward both the cell lines.A new benzyl-substituted p-xylyl-linked benzimidazolium salt and its Ag(I)-carbene complex were synthesized. Ag-complex evidenced a short Ag―Ag separation of 3.10(6) Å. Both the compounds were evaluated for anticancer potential against HCT 116 and HL 60 cancer cell lines.Display Omitted► A new benzimidazolium salt (1) and Ag(I)-NHC complex (2) were synthesized. ► Both, 1 and 2, were characterized by elemental, NMR and X-ray diffraction methods. ► Complex 2 displayed short Ag―Ag separations (3.10(6) Å). ► The in vitro anticancer activities of both compounds were investigated. ► Ag-complex showed exceptionally good anticancer activity.
Keywords: Ag―Ag separation; Ag(I)-carbene complex; N-heterocyclic carbene; HCT 116 cancer cells; HL 60 cancer cells;

A 1D polyoxometalate chain built from {Mo16Ni16P24} wheels: Synthesis, structure and magnetism by Li-Fu Wang; Zhan-Zhong Zhuang; Ze Chang; Bo-Yu Zhou; Tong-Liang Hu (70-74).
A 1D polyoxometalate chain has been constructed from a {Mo16Ni16P24} cluster linked by two {NiO6} edge-shared octahedrons. This chained molybdenum nickel phosphate, Na2[Ni(H2O)8][Ni2(H2O)6][(Mo16O32)Ni16(OH)8(H2PO4)4(HPO4)16(PO4)4(H2O)8]·14H2O (1), crystallizes under hydrothermal reaction and in the monoclinic space group C2/m. In the chain of 1, another {NiO8} polyhedron is capsulated in the {Mo16Ni16P24} wheel. Magnetism analysis shows that there are antiferromagnetic interactions in 1.A 1D polyoxometalate chain Na2[Ni(H2O)8][Ni2(H2O)6][(Mo16O32)Ni16(OH)8(H2PO4)4(HPO4)16(PO4)4(H2O)8]·14H2O constructed from a {Mo16Ni16P24} cluster has been synthesized under hydrothermal conditions. The magnetic studies reveal that antiferromagnetic interactions exist in the chain.Display Omitted► A 1D polyoxometalate chain has been constructed from a {Mo16Ni16P24} cluster. ► In the chain, another {NiO8} polyhedron is capsulated in the {Mo16Ni16P24} wheel. ► The magnetic properties of the reported compound have been investigated.
Keywords: Polyoxometalate chain; Crystal structure; Magnetism;

To assemble metal–organic coordination complexes, a flexible dicarboxylate ligand, 2,2′-(4,6-dimethyl-5-nitro-1,3-phenylene)bis(methylene)-bis-(sulfanediyl)dibenzoic acid (H2 L), has been designed and synthesized. Using the flexible ligand to assemble with copper ions, a mixture of two metal–organic complexes, Cu2(L)2(py)4·4dmso (1) and Cu2(L)2(py)6·3dmso·py (2), has been generated by solvothermal technology in one glass tube. Through increasing the mole fraction of pyridine, the pure phase of complex 2 was obtained. Both complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, and thermogravimetric analysis. Complex 1 is a discrete rectangular macrocycle. The guest solvents of dimethyl sulfoxide molecules were trapped in the cavity of rectangular metallmacrocycle, resulting in the formation of an infinite supramolecular metal–organic nanotube through van der Waals interactions between the guests and the host molecules. In complex 2, the flexible ligand adopts a syn conformation to assemble with copper ions to form an infinite one-dimensional zigzag chain.The structures of the two complexes vary from discrete metallamacrocycle to 1D zigzag chain with the flexible ligands that are in the syn conformation and the two complexes were gotten in the same glass tube. Because of the existence of the guest molecular, the metal-organic supramolecular nanotubes were formed.Display Omitted► Two new copper(II) coordination complexes based on a flexible dicarboxylate ligand were synthesized and characterized. ► The flexible ligands in the syn conformation assembled with Cu (II) generated discrete macrometallocycles and 1D zigzag chain subunits in the same glass tube. ► And through increased the mole fraction of pyridine, the pure phase of complex 2 was obtained. ► The metal-organic supramolecular nanotubes were formed because of the existence of the guest molecular.
Keywords: Flexible dicarboxylate ligand; Metallamacrocycle; Metal–organic nanotubes; Zigzag chain;

Duplex structure facilitated by aqua ligand in a copper(II) coordination polymer by Jayanta K. Nath; Yanhua lan; Annie K. Powell; Jubaraj B. Baruah (81-84).
The structural aspects and magnetic properties of a novel five-coordinated copper(II) coordination polymer derived from a carboxylate tethered naphthalimide ligand, namely 5-(1,3-dioxo-1H, 3H-benzo[de]isoquinolin-2-yl)-isophthalic acid are presented. The coordination polymer having monodentate carboxylate groups connecting the copper ions to form a spiral duplex structure shows anti-ferromagnetic property.The role of coordinated water molecules in a novel five-coordinated copper(II) coordination polymer having spiral duplex structure showing anti-ferromagnetic property is discussed.Display Omitted► A naphthalimide bearing coordination polymer of copper(II) having spiral duplex structure is presented. ► The orientations of the aqua-ligands in the chains are responsible for the formation of duplex structure. ► The penta-coordinated coordination polymer is weakly antiferromagnetic.
Keywords: Penta-coordinated copper(II); Duplex structure; Coordination polymer; Aqua-ligand; Naphthalimide; Anti-ferromagnetic;

A new 3D Keggin-POM based metal–organic framework of Cu and H2biim: Assembly and properties of fluorescence and electrochemistry by Zhenyu Shi; Jun Peng; Xia Yu; Yan Shen; Zheyu Zhang; Kundawlet Alimaje; Xiang Wang (85-89).
A new 3D Keggin-based metal–organic framework consisting of two kinds of Cu-H2biim chains, Cu10(H2biim)10(PW12O40)2(OH)4·5H2O 1 (H2biim = 2,2′-biimidazole), has been synthesized under hydrothermal conditions. The TGA and PXRD measurements show that the framework is stable after removal of the guest water molecules. In addition, the luminescent and electrochemical properties of 1 have also been investigated.A new 3D Keggin-based metal–organic framework with Cu···Cu interactions has been synthesized under hydrothermal conditions. Interestingly, two kinds of Cu-H2biim (H2biim = 2,2′-biimidazole) chains coexist in compound 1, which are linked together through polyanions.Display Omitted► A new 3D Keggin-based metal-organic framework has been synthesized. ► Two kinds of of Cu-H2biim chains with Cu(I)···Cu(I) interactions coexist. ► The luminescent and electrochemical properties of 1 have also been investigated.
Keywords: Keggin; Metal–organic framework; Hydrothermal synthesis; Electrochemical property;

Polymer-supported bis (2- hydroxylanyl) acetylacetone Schiff base ligand was prepared by reaction of bis (2- hydroxylanyl) acetylacetone with chloromethylated polystyrene in DMF. In the subsequent reaction of this polymer-supported Schiff base ligand with MoO2(acac)2 the polymer-supported bis (2- hydroxylanyl) acetylacetonato MoO2 Schiff base complex was prepared. This polymer-supported molybdenum Schiff base catalyst was highly active and selective in epoxidation of various alkenes in the presence of tert-buthyl hydroperoxide (TBHP) in CCl4. It can be recovered and reused for 8 times without any loss in its activity.Functionalized polymerstyrene bis (2- hydroxylanyl) acetylacetone Schiff base ligand and polymer-supported bis (2- hydroxylanyl) acetylacetonato MoO2 Schiff base complex were prepared. The supported molybdenum based Schiff base catalyst was highly active, selective and reusable in epoxidation of various alkenes in the presence of tert-buthyl hydroperoxide (TBHP) in CCl4.Display Omitted► Supported bis (2-hydroxylanyl) acetylacetone and its MoO2 complex were prepared. ► They characterized by NAA, CHN and FT-IR spectroscopy. ► Catalytic activity of supported complex was investigated in epoxidation reaction. ► It was highly active, selective and reusable catalyst.
Keywords: Polymer-support; Molybdenyl dication; Schiff base complex; Diimine complex; Epoxidation;

The novel α-Keggin heteropolyanion supramolecular compound based on organic ammonium and 18-crown-6, [(p-ClANH3)·(18-crown-6)]3·(PMo12O40)·(CH3CN) (1), has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV–vis, PXRD and 1H NMR (p-ClANH2  = p-chloroaniline). The rotator–stator assembly, [(p-ClANH3)·(18-crown-6)]+, was formed through dipolar donor–acceptor attractions, in which the guest p-ClANH3 + cation was projected towards the host 18-crown-6 cavity by strong N―H…O18-crown-6 H-bonds. The extensive and effective intermolecular hydrogen bonds, among/between organic rotator–stator assemblies and α-Keggin (PMo12O40)3 − anion clusters, connected the structural units into a 3D supramolecular functional architecture. In addition, the thermal analysis (TGA and DSC) and luminescent properties were investigated.The rotator–stator assembly, [(p-ClANH3)·(18-crown-6)]+, was formed through dipolar donor–acceptor attractions, in which the guest p-ClANH3 + cation was projected towards host 18-crown-6 cavity by strong N―H…O18-crown-6 H-bonds. The extensive and effective intermolecular hydrogen bonds, among/between organic rotator–stator assemblies and α-Keggin (PMo12O40)3 − anion clusters, connected the structural units into a 3D supramolecular functional architecture.Display Omitted► Macrocyclic cation assembly was formed through dipolar donor-accepter attractions. ► Guest cation was projected towards the host 18-crown-6 cavity by strong H-bonds. ► Cation and anion clusters were connected into a 3D supramolecular architecture.
Keywords: Anion cluster; Crystal structure; Hybrid complex; Macrocycle;

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) catalyzed esterification with 1-bromooctane over tetrakis/octakis(carboxy)phthalocyanines originated from trimellitic anhydride and pyromellitic dianhydride led to the isolation of a series of 2(3),9(10),16(17),24(25)-tetrakis(octyloxycarbonyl)phthalocyaninato metal complexes M[Pc(COOC8H17)4] (M=Co, Ni, Cu, Zn) (1a1d) and 2,3,9,10,16,17,24,25-octakis(octyloxycarbonyl)phthalocyaninato metal complexes M[Pc(COOC8H17)8] (M=Co, Cu) (2a, 2c). In addition to elemental analysis, these tetrakis/octakis(octyloxycarbonyl)-substituted phthalocyanines were characterized by a series of spectroscopic methods including MALDI-TOF mass, 1H NMR and 2D COSY, UV–vis, and IR spectroscopy. The tetrakis(octyloxycarbonyl)-substituted phthalocyanines represent the first example of 2(3),9(10),16(17),24(25)-tetrakis(octyloxycarbonyl)phthalocyaninato metal complexes that have ever been unambiguously characterized by mass and NMR spectroscopy.Tetrakis- and octakis-(octyloxycarbonyl)phthalocyaninato metal complexes isolated from trimellitic anhydride and pyromellitic dianhydride have been unambiguously characterized by a wide range of spectroscopic techniques, providing a reliable method for the synthesis of corresponding phthalocyanine compounds.Display Omitted► Phthalocyanines were synthesized from trimellitic anhydride/pyromellitic dianhydride. ► Synthesis octyloxycarbonyl substituted phthalocyanines by esterification reaction. ► Characterized by elemental analysis, MALDI-TOF mass, UV–vis, IR and NMR spectroscopy
Keywords: Octyloxycarbonyl; Phthalocyanine; Esterification; Trimellitic anhydride; Pyromellitic dianhydride;

A novel iron(II) complex, trans-[FeL2(NCS)2][FeL2(CH3OH)2](NCS)2 (1) with 4-amino-3-(p-chlorophenyl)-5-(2-pyridyl)-1,2,4-triazole (L) has been successfully synthesized and characterized. X-ray crystallography analysis shows that 1 is the first example in the mononuclear triazole-based complexes consisting of two distinct molecules: trans-[FeL2(NCS)2] and trans-[FeL2(CH3OH)2](NCS)2 with each octahedral iron(II) center coordinated axial by two NCS ions in Fe1 but two MeOH molecules in Fe2. Moreover, 1 can lose two MeOH molecules at 220 °C to form trans-[FeL2(NCS)2] (2) which can be transformed to 1 when recrystallizing 2 in methanol. Both 1 and 2 are high-spin species in the range of 1.8–300 K.A novel iron(II) complex, trans-[FeL2(NCS)2][FeL2(CH3OH)2](NCS)2 (1) has been synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is the first mononuclear triazole-based octahedral complex with two trans-coordinated NCS- ions and MeOH molecules. 1 reveals an interesting substitution of axial ligand NCS– for CH3OH when heated at 220 °C.Display Omitted► A new asymmetrical 3,5-disubstituted 1,2,4-triazole and its iron(II) complexes. ► Their structures were characterized by IR, ESI-MS, EA and X-ray crystallography. ► The first mononuclear triazole-based complex with two trans-positions NCS– and MeOH. ► A substitution of axial ligand NCS– for CH3OH in the complex occurs at 220 °C.
Keywords: Syntheses; Triazole; Crystal structures; Iron(II) complex; Ligand's substitution;