Inorganic Chemistry Communications (v.34, #C)

Contents (iii-viii).

HgBrI: A promising nonlinear optical material in IR region by Qi Wu; Yanjun Li; Huaichuan Chen; Kui Jiang; Hua Li; Cheng Zhong; Xingguo Chen; Jingui Qin (1-3).
This paper reports the second-order nonlinear optical (NLO) property of HgBrI for the first time. The compound was re-synthesized with a new synthetic method by combining the individual solution of stoichiometric amounts of HgBr2 and I2 in acetone. The compound exhibits a strong phase-matchable second harmonic generation (SHG) property about 1.4 times stronger than KTiOPO4 (KTP) based on the powder SHG measurement. It also shows wide transparency in the infrared region from 0.46 to 40 μm and good thermal stability with decomposition temperature at about 200 °C. All these properties indicate that HgBrI is a promising new candidate for NLO materials in the IR region.HgBrI was re-synthesized with a new method and characterized. It exhibits a phase-matchable second harmonic generation of about 1.4 times that of KTP. Display Omitted
Keywords: Halides; Synthesis; Crystal structure; Nonlinear optical materials; Infrared;

Three mercury complexes from a symmetric pentadentate ligand 2, 6-bis (8-quinolinyl thiomethyl) pyridine (L) have been prepared by the method of diffusing of diethyl ether or diisopropyl ether. The structures of the complexes have been identified by elemental analysis (EA), infrared spectra (IR) and single-crystal diffraction, and are composed of discrete mononuclear units in complexes 1 and 2 and binuclear units in complex 3. Especially, the valence of Hg in complex 3 is reduced to − 1 in-situ during self-assembly and Hg―Hg σ bond is formed, which is further evidenced by the frontier orbital and natural bond orbital (NBO) properties calculated by DFT method. The antibacterial and antifungal activities of the ligand and the three complexes were also determined, which prove foundation information for research and application in pharmaceutical chemicals.In the present work, three Hg(II) complexes [Hg(L)Cl2], [Hg(L)] · (ClO4)2 and [Hg2(L)2](ClO4)2  · H2O of 2, 6-bis (8-quinolinylthiomethyl) pyridine (L) have been prepared and structurally characterized. The microbial activity of the ligand and three Hg(II) complexes were determined.Display Omitted
Keywords: Mercury complexes; 2, 6-Bis (8-quinolinylthiomethyl) pyridine; DFT calculation; Antibacterial and antifungal activities;

Coumarin-hydrazone based high selective fluorescence sensor for copper(II) detection in aqueous solution by Hongxia Xu; Xiaoqing Wang; Changli Zhang; Yanping Wu; Zhipeng Liu (8-11).
In this article, a new coumarin-hydrazone based Cu2 + fluorescence sensor (L2) has been prepared. The sensor displays a rapid and a linear response to Cu2 + with a 6-fold turn-off signal with a K a of 0.1 μM in aqueous solution. L2 also shows a highly selective fluorescence response to Cu2 + over other transition metal ions. The intracellular Cu2 + imaging ability on MCF-7 cells demonstrates that L2 is an effective Cu2 + imaging agent.A new coumarin-hydrazone based fluorescent sensor (L2) for Cu2 + sensing has been developed. The sensor features a rapid and a linear response to Cu2 + with a 6-fold turn-off signal. UV–vis titration results indicate a 1:1 stoichiometry of L2/Cu2 + complex with a K a of 0.1 μM.Display Omitted
Keywords: Coumarin-hydrazone; Cu2 +; Fluorescent sensor; Imaging;

A 10-connected coordination network based on the planar tetranuclear cobalt cluster building blocks: synthesis, structure, and magnetism by Hai-Yan Cao; Qing-Yan Liu; Cai-Ming Liu; Yu-Ling Wang; Li-Li Chen; Li-Hua Xiong (12-14).
A coordination polymer [Co42-H2O)2(1,4-ndc)4(dpp)2]n (1) with the 1,4-naphthalenedicarboxylic acid (1,4-H2ndc) and 1,3-di(4-pyridyl)propane (dpp) mixed ligands has been synthesized and structurally and magnetically characterized. Compound 1 features a 3D framework based on the tetranuclear [Co42-H2O)2(COO)6] secondary building units (SBUs) where the four cobalt ions are coplanar. The 3D coordination network of 1 is a rare 10-connected network of (36·434·53·62) topology based on the tetranuclear cobalt cluster nodes. Magnetic measurements on compound 1 indicate that there is a net antiferromagnetic coupling among the Co(II) ions.A ten-connected coordination network [Co42-H2O)2(1,4-ndc)4(dpp)2]n has been synthesized and structurally and magnetically characterized.Display Omitted
Keywords: 10-connected network; Co(II) coordination polymer; (36·434·53·62) topology; Magnetism;

Novel magnetic CoII complexes: Synthesis and characterization by Yanchao Guo; Tao Shi; Zhenjun Si; Qian Duan; Linfang Shi (15-18).
Two CoII complexes of [Co(phen)2(H2O)(HL)OH] (1) and [Co(bpy)(H2O)(EtOH)L]n (2), where L = 4,4′-(2-acetylpropane-1,3-diyl)dibenzoic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine, were hydrothermally synthesized and characterized by the single crystal X-ray diffractions, the infrared spectroscopy, the thermogravimetric analyses, and the magnetochemical analyses. Complex 2 can form one dimensional coordination polymers with the help of bridge ligand of L2 −. Furthermore, both 1 and 2 can form the supramolecules through the intermolecular hydrogen bond interactions. The higher values of Tχm, 3.29 K · cm3/mol (g = 2.65, S = 3/2) at 300 K, reveal that there should be typical contribution of the orbital momentum for the 4T1g ground state of the CoII ions in complex 1.Two CoII complexes were hydrothermally synthesized, and their single crystal structures, thermal stabilities, and magnetism were fully studied.Display Omitted
Keywords: Single crystal structure; CoII complexes; Magnetism; Hydrothermal synthesis;

New oxime-derived palladacycles were prepared, spectral characterized, and immobilized on silica gel. Homogeneous catalysis indicates that pyridine coordinated oxime-derived palladacycles 1 and 2 were very effective in the methanolysis of fenitrothion, but suffered from the formation of the inactive dimmer at higher concentration. Immobilization of oxime-derived chloro-coordinated mononuclear and chloro-bridged dinuclear palladacycles afforded the high efficient and recoverable heterogeneous catalysts Si–Pd1 and Si–Pd2, both solid catalysts proved to be reusable in 10 runs and fascinated the degradation of a series of phosphorothionate pesticides up to 4.9 × 108 folds at s spH 8.8 and 25 °C.Immobilization of oxime-derived palladacycles afforded the high efficient and reusable heterogeneous catalysts for the degradation of a series of phosphorothionate pesticides.Display Omitted
Keywords: Palladacycle; Immobilization; Methanolysis; Phosphorothionates; Pesticides;

A novel compound based on saturated Wells–Dawson type phosphomolybdate, [Cu(H2O)4]3[P2Mo18O62]·12H2O (1) has been synthesized by the conventional solution method and characterized by elemental analysis, IR spectrum, UV spectrum, thermogravimetric analysis, electrospray ionization mass spectrometry (ESI-MS), electrochemistry and single-crystal X-ray diffraction. X-ray structural analysis reveals that 1 exhibits the 6-connected 2D topological network with the Schläfli symbol of (3649).A novel compound based on saturated Well-Dawson type phosphomolybdates [Cu(H2O)4]3[P2Mo18O62]·12H2O (1) which exhibits a 2D network constructed from [P2Mo18O62]6– interconnected through [Cu(H2O)4]2+ bridging, has been synthesized by the conventional solution method. 1 exhibits the electrochemical behavior.Display Omitted
Keywords: Phosphomolybdate; Wells–Dawson; Electrochemical behavior; Inorganic cluster;

Hydrothermal reaction of Sr(II) salt with the promising multifunctional organic ligand, 2-(3,4-methylenedioxyphenyl)-1H-imidazole-4,5-dicarboxylic acid (MDPhH3IDC), leads to one new Sr(II) polymer, namely [Sr(MDPhH2IDC)2(H2O)3]n (1), which has been structurally characterized by elemental analysis, IR spectrum, and single crystal X-ray diffraction analysis. In polymer 1, the Sr(II) atoms are linked by water ligands to develop many 1-D chains. These chains are further joined by the MDPhH2IDC ligands to build up a fascinating 3-D structure. Interestingly, the polymer contains many dinuclear Sr(II) clusters as secondary building blocks. The thermal and photoluminescence properties of the polymer have been investigated as well.One Sr(II) polymer has been successfully isolated from the reaction of 2-(3,4-methylenedioxyphenyl)-1H-imidazole-4,5-dicarboxylic acid (MDPhH3IDC) with equal amount of Sr(II) salt under hydrothermal condition. It has been structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction.Display Omitted
Keywords: Imidazole dicarboxylate; Strontium; Polymer; Crystal structure;

The path of the chirality delivery in the crystalline and chiral nucleotide–Co(II) complex, [Co(GMP)(H2O)5]·3H2O (GMP = guanosine-5′-monophosphate), has been studied based on X-ray single crystal diffraction analysis, liquid- and solid-state circular dichroism (CD) spectroscopy. The multiple and helical H-bonding is a distinctive way of chirality delivery from the discrete molecules to three-dimensional supramolecular architecture.The molecular chirality of crystallized nucleotide-transition metal coordination complex is delivered to three-dimensional supramolecular architecture through multiple and helical H-bonding in its crystal lattice. Liquid- and solid-state CD spectroscopy confirm the novel path of chirality delivery.Display Omitted
Keywords: Chirality delivery; Circular dichroism; Nucleotide complex; Supramolecular architecture;

One new title compound [Mn3(BIBP)(sdb)(NO2 )2(H2O)2] n ·2DMF (1) (BIBP = 4,4′-bisimidazolylbiphenyl, sdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction. Magnetic susceptibility measurements indicate that compound 1 exhibits antiferromagnetic coupling interaction.One new compound [Mn3(BIBP)(sdb)(NO2 )2(H2O)2] n ·2DMF has been synthesized under hydrothermal condition. The compound has an interesting 3D architecture which can be simplified α-Po pcu net with topology symbol {412⋅ 63}Display Omitted
Keywords: Biimidazole; Aromatic carboxylic acids; Crystal structure; Coordination polymer;

Under similar hydrothermal synthetic conditions using a novel flexible ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetonitrile (PPAN), benzenedicarboxylate isomers (H2pa = phthalate, H2ip = isophthalate, and H2tp = terephthalate) and Cadmium(II) acetate, three novel mixed-ligand Cd(II) coordination polymers {[Cd2(PPAA)2(μ-pa)(H2O)]·2H2O} n (1), {[Cd4(PPAA)44-ip)2]·2H2O} n (2) and {[Cd2(PPAA)2(μ-tp)]·2H2O} n (3) (PPAA  = 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetate) have been isolated, in 13 PPAN, and are also hydrolyzed into a novel PPAA ligand. Complex 1 is a 1D coordination polymer in which the tetra-nuclear [Cd4(PPAA)4]4 + structural units are extended by tri-dentate μ-pa2 − ligands. Complex 2 contains binuclear [Cd2(PPAA)2]4 + structural units, which are extended by four tetra-dentate μ4-ip2 − ligands to link eight neighboring binuclear [Cd2(PPAA)2]4 + units ultimately forming a 2D layered framework, while complex 3 contains 1D double chain containing [Cd(PPAA)] n cation structural units, which are further extended by tetradentate μ-tp2 − ligands to form a new 2D layered framework. All the complexes have been investigated by elemental analysis, FT-IR, thermal analysis and fluorescence characterization. The flexible coordination modes of PPAA are also briefly analyzed. The flexible coordination modes of PPAA and benzenedicarboxylate isomers also reveal great potential in the construction of these novel mixed-ligand luminescent frameworks with diverse structural motifs and unique functional properties.This work presents three fluorescent Cd(II) coordination polymers based on a novel 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetate and different benzenedicarboxylate isomers (phthalate, isophthalate, and terephthalate), which exhibit distinct 1D chain and 2D layered coordination arrays.Display Omitted
Keywords: PPAA; Mixed-ligand; Clusters; Luminescent;

A highly sensitive and selective fluorescent probe for Hg2 + and its imaging application in living cells by Zhi-Hong Xu; Xu-Feng Hou; Wen-Lei Xu; Rui Guo; Tian-Cheng Xiang (42-46).
Two rhodamine-based Hg2 + probes L1 and L2 were prepared and confirmed by NMR, MS and crystal data. The sensing behavior of these probes was studied by UV–visible and fluorescence spectroscopy. The probe L1 couldn't be widely applied in aqueous media or mixed media because of its poor solubility. However, the probe L2 displayed selective and sensitive fluorescence enhancement response to Hg2 + at physiological pH value for biological use. The selectivity of this system for Hg2 + over other metal ions was remarkably high, and its sensitivity was at ppb level. The probe L2 responded rapidly to Hg2 + in aqueous solutions with a 1:1 stoichiometry and was successfully applied to image Hg2 + in living cells.Two rhodamine-based Hg2+ probes L1 and L2 were synthesized and characterized. The probe L1 can't be applied because of its poor solubility. However, the probe L2 shows a high selective and sensitive fluorescence response to Hg2+. Furthermore, the L2 was successfully used for the detection of Hg2+ in living cells.Display Omitted
Keywords: Fluorescent probe; Rhodamine derivatives; Hg2 +; Imaging application;

A zinc-organic coordination polymer of glycine-functionalized naphthalenediimide ligand by Lan Qin; Wen-Na Zhao; Guo-Jun Yu; Lan-Ping Xu; Lei Han (47-50).
The first metal–organic coordination polymer of amino-acid functionalized naphthalenediimide (NDI) ligand, [Zn(Gly-NDI)(DMF)2] n (1), has been synthesized and characterized. Single-crystal X-ray diffraction revealed that the Zn ions are linked by anti-conformational Gly-NDI ligands, and 1 displays a one-dimensional zigzag chain coordination polymer. These chains are cross-linked through strong π···π stacking interactions between NDI cores to give a three-dimensional supramolecular framework with square planar 4-connected CdSO4 (cds) topology. The thermal stability and fluorescence emissions of 1 were also investigated.The zigzag chains of 1D coordination polymer based on glycine-functionalized naphthalenediimide ligand are cross-linked through strong π···π stacking interactions to give a 3D supramolecular framework with square planar 4-connected CdSO4 (cds) topology.Display Omitted
Keywords: Coordination polymer; Naphthalenediimide; Glycine; CdSO4 (cds) topology;

A new zinc coordination polymer [Zn(L)2]n (1) (HL = 4′-(4-carboxy-methoxyphenyl)-4,2′:6′,4″-terpyridine) was constructed under hydrothermal condition. X-ray single diffraction studies reveal that 1 shows a three-fold interpenetrating 3D framework with a 4-connected dia topological net, which contains the same number of left- and right-handed 21 helical chains. Additionally, photoluminescence property of 1 has been investigated.A new 3D Zn(II) coordination polymer with a new semi-rigid tripodal ligand tecton shows 4-connected three-fold interpenetrating diamond network with helical character and strong photoluminescence.Display Omitted
Keywords: Coordination polymer; Terpyridine derivative; Helical chain; Interpenetration; Luminescent property;

Syntheses, structures and luminescent properties of two organic templated uranyl phosphonates by Hong-Yue Wu; Yu-Qin Ma; Xiuwu Zhang; Hongwei Zhang; Xiu-Yun Yang; Yun-Hui Li; Hao Wang; Shuang Yao; Weiting Yang (55-57).
Two organic templated uranyl phosphonates (Hbpi)[(UO2)2(H2O)(PO3C6H5)2(HPO3C6H5)] (1) and (H2dib)0.5[UO2(H2O)(Hhedp)] (2) (bpi = 1-([1,1′-biphenyl]-4-yl)-1H-imidazole, dib = 1,4-di(1H-imidazol-1-yl)butane, H4hedp = 1-hydroxyethylidenediphosphonic acid), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR and photoluminescent spectroscopy. The structures of compounds 1 and 2 have been determined to be layered structures constructed by UO7 pentagonal bipyramids and PO3C tetrahedra of phenylphophonate and hedp groups, respectively. Adjacent layers are packed in AA stacking into the supramolecular structure, in which protonated bpi and dib molecules fill and compensate the negative charge of 1 and 2, respectively. Photoluminescence studies indicate that the two complexes exhibit characteristic green light emission of uranyl cations.Two new organic templated uranyl phosphonates, (Hbpi)[(UO2)2(H2O)(PO3C6H5)2(HPO3C6H5)] (1) and (H2dib)0.5[UO2(H2O)(Hhedp)] (2) (bpi = 1-([1,1′-biphenyl]-4-yl)-1H-imidazole, dib = 1,4-di(1H-imidazol-1-yl)butane, H4hedp = 1-hydroxyethylidenediphosphonic acid) are hydrothermally synthesized. Both layered structures feature the UO7 pentagonal bipyramid and PO3C tetrahedra of the two phosphonate ligands. Photoluminescence studies indicate that the two complexes exhibit characteristic emission from UO2 2 + cations.Display Omitted
Keywords: Uranyl; Phosphonates; Template; Structure; Luminescence;

One new organic–inorganic hybrid solid salt, [(pbmH)2] [WO2F4] (1) (pbm = 2-(2-hydroxyphenyl)benzimidazole), containing tungsten oxide fluoride anion [WO2F4]2 −, and organic cation, pbmH+, has been synthesized via solution-based self-assembling technique and characterized structurally. The geometric structure and electronic structure of [WO2F4]2 − anion have been calculated, and discussed in detail by the density functional theory levels (DFT), the partial density of states (PDOS) and the overlap population density of states (OPDOS) analyses. The experimental results are well comparable to those of theoretical ones. The observed crystal stacking and structure-directing properties of [WO2F4]2 − anion in crystalline 1 are well interpreted. Furthermore, the distortion of [WO2F4]2 − octahedron, the variation trend of bonding distances of W―O/F atoms, and the structure-directing properties of [WO2F4]2 − anion, together with their inter-relationships have been well discussed.One new organic-inorganic hybrid solid salt, [(pbmH)2][WO2F4] (1) (pbm = 2-(2-hydroxyphenyl)benzimidazole) was synthesized via self-assembling technique, calculated/discussed by DFT method, PDOS and OPDOS analyses. The crystal stacking, structure-directing properties, structure distortion, the variation trend of bonding distances of [WO2F4]2– anion, together with their inter-relationships, are well interpreted and discussed.Display Omitted
Keywords: Structure-directing; Crystal structure; Calculation; Electronic structure; DFT; Tungsten oxide fluoride;

Two bistetrazolato complexes cis-[Co(5-phenyl-tetrazolato)2(en)2](NO3) (1) and trans-[Co{5-(4-chlorophenyl)-tetrazolato}2(en)2]NO3 (2) have been synthesized starting from the diazide cobalt complex [Co(N3)2(en)2]NO3 and two different organonitriles using microwave irradiation technique. It has been found that the remote substitution at 4-position of phenyl ring exhibits an influence on the geometrical preference of cycloadded metal complex. Theoretical investigation revealed that compound 1 is a kinetic product whereas stability of compound 2 has been driven by extra thermodynamical stability out of additional halogen–halogen interaction.Display Omitted
Keywords: Cobalt Complex; Cycloaddition; Tetrazoles; Geometrical isomers; DFT;

A new 3D helical silver(I) cluster metal–organic framework with microporous structure and luminescent property by Jun-Cheng Jin; Wen-Gui Chang; Jian-Qiang Liu; Cheng-Gen Xie; Ju Wu (68-70).
A new 3D helical silver(I) metal–organic polymer of {[Ag2(ADC)(bib)0.5]·H2O}n (1) (H2ADC = 1,3-adamantanedicarboxylic acid, bib = 1,4-bis(2-methyl-imidazol-1-yl)butane), has been synthesized and characterized. Compound 1 exhibits significant void space that may be filled with guest H2O molecules in spite of the metal-cluster that occurs in the solid. Preliminary thermal and fluorescence experiments show that compound 1 possesses strong fluorescent property and thermal stability, respectively.An new 3D helical silver(I) metal-cluster coordination polymer {[Ag2(ADC)(bib)0.5]·H2O}n (1) (H2ADC = 1,3-adamantanedicarboxylic acid, bib = 1,4-bis(2-methyl-imidazol-1-yl)butane), has been synthesized. It exhibits significant void space that may be filled with guest H2O molecules in spite of the metal-cluster that occurs in the solid. Besides, this compound also exhibits high thermal stability and blue-shift emission, and can be explored for potential blue luminescent materials.Display Omitted
Keywords: Crystal engineering; Silver cluster; Helical structure; Fluorescence spectrum;

A new three-dimensional supramolecular framework based on 1,4-bis(5,6-dimethylbenzimidazole)butane (L) with 5-hydroxyisophthalic acid (H2hip) has been synthesized by hydrothermal reaction, namely, [Co(L)0.5(hip)] n , exhibiting an unprecedented topology architecture through hydrogen bonds, viz. supramolecular net 4-connected uninodal 3D net with (65⋅8) msw/P42/nnm topology. The fluorescence and remarkable catalytic performances of the complex for the degradation of methyl orange by sodium persulfate have been investigated.A new supramolecular framework has been constructed by the assembly of CoII center with flexible benzimidazolyl-based ligand and 5-hydroxyisophthalate, which features a unique msw-P42/nnm topology. The results of catalytic experiment show that the complex presents high efficiency as a heterogeneous catalyst for the degradation of methyl orange in Fenton-like process.Display Omitted
Keywords: Bis(benzimidazolyl)butane; Hydrogen bonds; Degradation; Supramolecular framework;

The molecular linkage (phenSi) is modified from 5-amino-1,10-phenanthroline (phenNH2) by 3-(triethoxysilyl)-propyl isocyanate (TESPIC). Then phenNH2 functionalized periodic mesoporous organosilica (PMO) hybrids are synthesized by linking ternary europium complexes with phenSi linkage and 2-methyl-9-hydroxyphenalenone (MHPO), which use co-condensation method in the presence of Pluronic P123 surfactant as a template. The europium PMO hybrid system (denoted as Eu(MHPO)3phen-PMO(NO3)3) has been characterized in detail, whose results reveal that these hybrids have uniformity in the mesopore structure. It is worthy pointing out that the europium hybrids show emission of both europium ion and phen functionalized PMOs, which can be integrated into the close white luminescence. This provides us a strategy to obtain white emissive lanthanide hybrids.Functionalized periodic mesoporous organosilica (PMO) hybrids show emission of both europium ion and phen functionalized PMOs, which can be integrated into the close white luminescence.Display Omitted
Keywords: Organic–inorganic hybrids; Periodic mesoporous organosilica; Ternary europium complex; Photoluminescence; White color;