Inorganic Chemistry Communications (v.50, #C)

Contents List (iii-x).

Bis-o-semiquinonato cadmium(II) complexes with o-quinonato and N-heterocyclic carbene neutral ligands by Ekaterina V. Bellan; Andrey I. Poddel'sky; Natalia A. Protasenko; Anton V. Cherkasov; Artem S. Bogomyakov; Vladimir K. Cherkasov; Gleb A. Abakumov (1-3).
The reaction of cadmium amalgam with excess of 3,6-di-tert-butyl-o-quinone (3,6-Q) in THF afforded the new bis-o-semiquinonato cadmium(II) complex coordinated with one molecule of neutral o-quinone (3,6-SQ)2Cd(3,6-Q) (1) acting as a starting reagent to other bis-o-semiquinonato cadmium(II) complex with N-heterocyclic carbene (NHC)–(3,6-SQ)2Cd{C[N(Ar)(CH)]2} (Ar = 2,6-dimethylphenyl) (2). Both complexes possess a singlet ground state with thermally accessible triplet state (the singlet-triplet gap is 8 cm− 1 for 1 and 132 cm− 1 for 2) as confirmed by magnetic data. The antiferromagnetic exchange SQ–SQ is observed for both complexes.The new bis-o-semiquinonato cadmium(II) complexes with o-quinonato and N-heterocyclic carbene neutral ligands were obtained. Both complexes possess a singlet ground state with thermally accessible triplet state as confirmed by the magnetic data. The antiferromagnetic exchange SQ–SQ is observed for both complexes.Display Omitted
Keywords: Redox-active ligands; o-Semiquinone; Cadmium; N-heterocyclic carbene; X-ray analysis;

Novel [(UO2)O6(NO3) n ] (n  = 1, 2) based units in organically templated uranyl compounds by Oleg I. Siidra; Evgeny V. Nazarchuk; Anastasiya I. Zadoya (4-7).
Two novel organically templated (CH3)2(NH2)2[(UO2)2(NO3)2(CrO4)2(H2O)]H2O (1) and (15-crown-5)2[(UO2)2(H2O)4(O2)(NO3)2](H2O)3.5 (2) compounds were obtained at room temperature in chromate containing systems from aqueous solutions. The structure of 1 is the first observation of one-dimensional unit (chain) with two different (UO2)2+ coordination geometries (UrO5, UrO6) in uranyl oxocompounds with TO4 tetrahedral oxoanions. 2 is rare example of organically templated uranyl compound containing peroxide component with neutral organic and inorganic constituents.Two novel uranyl compounds with [UO8(NO3) n ] (n  = 1, 2) based structural units.Display Omitted
Keywords: Uranium; Coordination modes; Nitrate; Chromate; Peroxide; Crown-ethers; Organically templated compounds;

A novel lanthanide coordination polymer, (H2pipz)3[Tb2(pydc)6]·15H2O (1) (where pipz = piperazine and H2pydc = pyridine-2,6-dicarboxylic acid), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, element analysis and thermogravimetric analysis. The most interesting structural feature of 1 consists in the occurrence of one-dimensional infinite water chains made up of novel (H2O)20 clusters. 1 is extended into a three-dimensional supramolecular network structure via an extensive net of hydrogen bonds together with π–π stacking interactions. In addition, 1 was demonstrated to display a green fluorescence emission in the solid state at room temperature.A novel (H2O)20 cluster encapsulated in the lattice voids of the lanthanide coordination polymer, (H2pipz)3[Tb2(pydc)6]·15H2O (where pipz = piperazine and H2pydc = pyridine-2,6-dicarboxylic acid) formed a one-dimensional infinite water chain through hydrogen bonding.Display Omitted
Keywords: Lanthanide coordination polymer; Crystal structure; Water clusters; Luminescent property;

Enhanced DSSC performance with tri-pyridine-ruthenium heteropolytungstate by Chun-Hui Shan; Xiao-Jing Sang; Hong Zhang; Jian-Sheng Li; Wei-Lin Chen; Zhong-Min Su; En-Bo Wang (13-16).
In this paper, we load TiO2 on the surface of the tri-pyridine-ruthenium heteropolytungstate [Ru(bipy)3]2[SiW12O40]·2C2H5OH·8H2O (1), which is mixed with P25 powder to get photoanode material and then adsorb N719 dyes to assemble a dye-sensitized solar cell. It is important that the performance of the DSSCs with 1-doped TiO2 (1 @ TiO2) is superior to ones with H4SiW12O40-doped TiO2 ({SiW12} @ TiO2), although their photoelectric conversion efficiencies are both higher than pure P25-based cells. The investigation of the EIS shows that 1 @ TiO2 can restrain charge recombination and doping the transition metal ruthenium improves the performance of the cell. The photovoltaic performance of the cell is enhanced and the short-circuit photocurrent density (J sc) is as high as 16.272 mA cm− 2, which is 20.4% higher than pure P25-based cells and 4.4% higher than the {SiW12} @ TiO2-based cells under simulated AM 1.5 irradiation.Tri-bipyridine-ruthenium heteropolytungstate has been successfully doped into TiO2 as photoanode in dye-sensitized, which improved the short-circuit photocurrent density (16.272 mA· m− 2) and open circuit voltage (704 mV).Display Omitted
Keywords: Polyoxometalate; Pyridine ruthenium; TiO2; Dye-sensitized solar cell;

Facile alternative route to cis-[PtCl2(PTA)2] and [PtCl(PTA)3]Cl (PTA = 1,3,5-triaza-7-phosphaadamantane) by Marina Ya. Demakova; Konstantin V. Luzyanin; Galina L. Starova; Vadim Yu. Kukushkin (17-18).
The reaction of trans-[PtCl2(Me2SO)2] with 2 equivs of 1,3,5-triaza-7-phosphaadamantane (PTA) in MeNO2 at RT furnished cis-[PtCl2(PTA)2] (1) in 87% isolated yield. Corresponding reaction of K2[PtCl4] with 1 equiv. of PTA in aqueous EtOH at RT led to [PtCl(PTA)3]Cl (2) in 84% isolated yield. Complexes 1 and 2 were characterized by elemental analyses (C, H, N), HR-ESI+/−-MS, IR, 1H and 31P{1H} NMR spectroscopic techniques, and by single-crystal X-ray diffraction for 1.Alternative procedure for the preparation of cis-[PtCl2(PTA)2] and [PtCl(PTA)3]Cl that starts from the widely available and non-toxic precursors has been developed.Display Omitted
Keywords: Platinum(II) complexes; 1,3,5-Triaza-7-phosphaadamantane; Ligand substitution;

A 3-D framework based on mono-copperII substituted silicotungstate units [Cu(dap)2(H2O)]2[Cu(dap)2][α-SiW11CuO39]·2H2O by Jie Luo; Hailou Li; Xinxin Chen; Jianru Ma; Lijuan Chen; Junwei Zhao (19-23).
A 3-D mono-copperII substituted silicotungstate [Cu(dap)2(H2O)]2[Cu(dap)2][α-SiW11CuO39]·2H2O (1) has been hydrothermally synthesized by reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, LaCl3 and dap (dap = 1,2-diaminopropane) and characterized by elemental analyses, IR spectrum, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. To our knowledge, 1 represents the first 3-D four-connected framework with the Schläfli symbol of 64  · 8 · 10 that is built by mono-copperII substituted silicotungstate units in polyoxometalate chemistry. The TG curve of 1 indicates two steps of weight loss between 25 and 750 °C. Furthermore, the solid-state electrochemical and electro-catalytic properties of 1 have been measured in 0.5 mol·L− 1 Na2SO4  + H2SO4 aqueous solution by entrapping it in a carbon paste electrode. 1 displays evident electro-catalytic activities toward the nitrite and bromated reduction.A 3-D four-connected framework with the Schläfli symbol of 64  · 8 · 10 that is built by mono-copperII substituted silicotungstate units has been synthesized and characterized.Display Omitted
Keywords: Polyoxometalate; Silicotungstate; 3-D framework; Electrocatalysis;

Fluorescent chemosensor based on pyrrole-aminoindanol for selective zinc detection by Jung Hee Choi; Ji Yeon Ryu; Yu Jin Park; Halima Begum; Hyoung-Ryun Park; Hee Jin Cho; Youngjo Kim; Junseong Lee (24-27).
A chemosensor for selective detection of zinc has been prepared by the simple one-step reaction of pyrrole-2-carboxaldehyde and amino indanol. Whereas other metal ions except Zn2 + have no effect on the fluorescence of it, Zn2 + enhanced the fluorescence at 400 nm by the complexation of the sensor molecule and Zn2 + ion. The chemosensor has high selectivity and sensitivity toward Zn2 + ion with high binding constant (3 × 106  M− 1) and low detection limit (1.0 × 10− 6  mol/L). 1H NMR spectroscopy and Job's plot suggest that they formed 1:1 complex.A fluorescence chemosensor has been prepared and exhibits high selectivity and sensitivity toward Zn2+ ion with high binding constant and low detection limit. Display Omitted
Keywords: Luminescent probe; Zinc; Schiff base; Tridentate; Detection;

Synthesis and reactivity of closo-decaborate anion derivatives with multiple carbon–oxygen bonds by I.N. Klyukin; A.P. Zhdanov; E.Yu. Matveev; G.A. Razgonyaeva; M.S. Grigoriev; K.Yu. Zhizhin; N.T. Kuznetsov (28-30).
Some methods of functionalization of closo-borate anions on the example of the interaction with carboxylic acids are considered. Oxonium derivatives of closo-decaborate anion [2-B10H9OC(OR)CH3] (R = H, Et) were prepared and transformed upon subsequent heating into 2,6-disubstituted derivative [2,6-B10H8(O2CCH3)]. The obtained compounds were characterized by IR and NMR (1H, 11B, 13C) spectroscopies. The crystal structure of (Bu4N)[2,6-B10H8(O2CCH3)] was determined by X-ray diffraction.The interaction between the anion [B10H11] and carboxylic acids and esters has stepwise nature. The first step leads to monosubstituted products with equatorial located substituent, that forms as a result of nucleophilic attack of the carbonyl oxygen of reagent. The second stage is conducted at ca. 100 °C resulting in the formation of 2,6-disubstituted product [2,6-B10H8O2CCH3].Display Omitted
Keywords: Closo-decaborate; Acyl derivatives; Disubstituted derivatives; Multiple carbon–oxygen bonds;

A terbium-based time-resolved luminescent probe for sulfide ions mediated by copper in aqueous solution by Yanmeng Xiao; Yanqin Yang; Guiyan Zhao; Xinxiu Fang; Yongxia Zhao; Pengran Guo; Wei Yang; Jingwei Xu (31-34).
A novel Tb(III) complex-based time-resolved luminescent probe, BBPNA-(DO3A-Tb3 +)2 (L), was designed and synthesized for the recognition of Cu2 + and sulfide ions in aqueous solutions. The luminescent probe L was efficiently quenched by Cu2 + and displayed “on–off” type luminescence change towards Cu2 +. Once combined with Cu2 + to form the non-luminescent LCu complex, the LCu complex could serve as an “off–on” probe for sulfide ions due to the high affinity of sulfide ions towards Cu2 +. In the presence of S2−, the LCu complex reacted with S2− to cause the release of the Cu2 + and turn on the luminescence of L again. The rebuilding of luminescence was highly selective to S2− over other common anions, which allowed L function as an “on–off–on” probe for Cu2 + and S2− alternately. Especially, the luminescence lifetime of the probe was about 1.91 ms, much longer than most organic fluorophores. Due to the long luminescence lifetime of the probe L, the probe could be used for time-resolved luminescence measurements to eliminate the interferences from autofluorescence and scattering lights and significantly to improve the signal-to-noise for detection.We designed an “on–off–on” water-soluble Tb3 +-based time-resolved luminescence probe for Cu2 + and S2− alternately in aqueous solutions, which could be used for time-resolved luminescence measurements.Display Omitted
Keywords: Time-resolved; BBPNA-(DO3A-Tb3 +)2; Luminescence lifetime; Signal-to-noise;

The ternary copper(II) complex with 1,10-phenanthroline and Schiff base derived from 2-amino-4-fluorobenzoic acid and salicylaldehyde, was synthesized and characterized by IR and 1H NMR spectroscopy, elemental analysis, and single crystal X-ray diffraction. X-ray crystallography shows that the copper atom adopts square pyramidal geometry and is five coordinated by the nitrogen atom from ―C=N―, two nitrogen atoms from 1,10-phenanthroline, the hydroxyl oxygen atom and the carboxylate oxygen atom. Our studies on the anticancer activity of the complex indicate that the complex can inhibit the cellular proliferation in human breast cancer MDA-MB-231 cells. In addition, it has proteasome-inhibitory activity in human breast cancer MDA-MB-231 cells. The inhibition of the tumor proteasomal activity results in the accumulation of ubiquitinated proteins and ubiquitinated form of IκB-α, a natural proteasome substrate, followed by induction of apoptosis. The results suggest that the title complex, as a potent proteasome inhibitor, has potential to be developed into a novel anticancer drug.3D structure of the Cu(II) complex. All hydrogen atoms and free solvent (methanol) molecules are omitted for clarity, except for those engaged in hydrogen bonding.Display Omitted
Keywords: Schiff base; Copper(II) complex; Crystal structure; Anticancer activity; Proteasome inhibitor;

Solvothermal reaction of conjugated pyridine/benzene dicarboxylic acid ligand with manganese acetate in the presence of ammonium oxalate afforded a novel 2D polymer, {[Mn4(ddpp)2 (μ 4-C2O4)·6H2O]·2H2O}n (ddpp = 2, 5-di(2′,4′-dicarboxylphenyl) pyridine) (1). It has been characterized by element analysis, thermogravimetry, infrared spectroscopy and single-crystal X-ray diffraction studies. Polymer 1 is constructed from tetranuclear MnII clusters through oxalate bridging, in which four adjacent MnII ions are linked into a parallelogram-core aggregate, and the polymer 1 exhibits 1D double-zigzag chains bearing a ladder-like topology feature. The ddpp ligands further interconnect these 1D double chains into 2D corrugated-shape network. Variable temperature magnetic susceptibility measurements indicate that polymer 1 exhibits weak antiferromagnetic interactions.A novel MnII polymer containing both the ddpp and oxalate auxiliary ligand has been synthesized. It displays high thermal stability and weak antiferromagnetic interactions between adjacent MnII ions.Display Omitted
Keywords: Oxalate bridging; Manganese (II) complex; Tetranuclear cluster; Anti-ferromagnetic interactions;

The two dinuclear complexes [Cu2(LMeO-tmpa)(OAc)2]PF6·H2O (1) and [Cu2(LMeO-tmpa)(N3)2]ClO4 (2), where LMe-OH-tmpa = 2,6-bis[bis(pyridine-2-ylmethyl)aminomethyl]-4-methylphenol, were synthesized and structurally and magnetically characterized. The five-coordinate geometry around the Cu(II) centers is achieved through the monodentate-acetato or -azido groups, the three N-donors of the ligand and a bridged-phenoxdio group. The two complexes reveal weak antiferromagnetic interaction.The two complexes [Cu2(LMeO-tmpa)(OAc)2]PF6·H2O (1) and [Cu2(LMeO-tmpa)(N3)2]ClO4 (2) have been synthesized and structurally characterized. The complexes reveal weak antiferromagnetic coupling.Display Omitted
Keywords: Copper; Polynuclear complexes; Bridged phenolate; Crystal structure; Magnetic properties;

2,6-Bis(8′-quinolinyl)pyridine (bqp) reacts with cobalt (II) acetate tetrahydrate in methanol with subsequent oxidation to give mer-[Co(bqp-κ3 N,N′,N″)2](Br3)3 . X-ray crystallographic data on mer-[Co(bqp-κ3 N,N′,N″)2](Br3)3 show that the bqp ligands achieve a mutually meridional arrangement and adopt a twisted, near-octahedral arrangement relative to the cobalt center. UV–vis absorption and cyclic voltammetry data suggests that the complex is highly promising for applications in a DSSC. Electronic and structural characteristics are supported by DFT calculations.Display Omitted
Keywords: 2,6-Bis(8′-quinolinyl)pyridine; Cobalt; Cyclic voltammogram; X-ray structure; DFT calculations;

The reactions of Cd(NO3)2⋅4H2O, Co(NO3)2.6H2O with nicotinic acid and 1,2-Di(4-pyridyl) ethylene under hydrothermal reaction conditions resulted in a metal-organic polymer [(H2O)Cd(C6H4O2N)2] 2[(C6H4O2N)2Co(H2O)2] 1. The compound 1 is the first nicotinato-linked mixed cobalt–cadmium compound displaying a square basket-like thick covalent 2-D layer structure.Although many structures containing nicotinato bridges have been reported, the nicotinato structural linkages with mixed cobalt and cadmium metal centers in constructing network structures remain unexplored. Herein we report a novel double cadmium-nicotinato linked square-basket metal-organic polymer displaying a thick covalent 2-D layer structure containing six mixed Cd and Co metal centered rings: [(H2O)Cd(C6H4O2N)2]2 [(C6H4O2N)2Co(H2O)2] 1, the first nicotinato linked cadmium and cobalt mixed metal centered coordination polymer with distinct basket-like features and entangled thick layers. The fused four-metal-centered ring are showing square basket-like shape that are linked by two Cd-nicotinato bridged chains on the side when it is viewed down to the b axis, which ultimately resulted in a novel thick 2-dimensional covalent layer network structure. The Cd-nicotinato bridging chains in the two-dimensional network displayed six metal-centered rings that facilitate the complexity of the thick layer. The systematic research on the mixed metal coordination polymers is underway in our laboratory.Display Omitted
Keywords: Coordination polymers; Crystal structure; Mixed metal complexes; Cobalt and cadmium; Hydrothermal reactions;

The self-assembly of Ru2(CO3)4 3−   and Zn2 + in neutral aqueous solution forms heterometallic carbonate ZnHRu2(CO3)4(H2O)2·2H2O (1). X-ray crystallographic analysis and magnetic investigation show that 1 behaves as 2D antiferromagnetic layers. It is different from those light transitional metal d1–9 centers (Mn, Co, and Ni), which merely exhibit octahedral MO6 environment and trans- or cis-mode link Ru2 dimers to form 2D and 3D frameworks, the production of 1 shows Zn2 + adopting tetrahedral environment. Compared with Zn2 + adopting octahedral environment in KZn(H2O)6[Zn(H2O)2Ru2(CO3)4Cl2]·4H2O, it proves that the axial position ligands (L) of Ru2 dimers account for the tetrahedral ZnO4 (L = H2O) or octahedral ZnO6 (L = Cl) environments, and this is also due to the d10 electronic configuration of Zn2 + with the equivalent crystal field energy of the tetrahedral ZnO4 and octahedral ZnO6 symmetry.Ru2(CO3)4 3− units are linked by tetrahedral Zn2 + forming heterometallic layer of {ZnHRu2(CO3)4(H2O)2} n , and it proves that the axial position ligands (L) of Ru2 dimer account for the tetrahedral ZnO4 (L = H2O) or octahedral ZnO6 (L = Cl) environments.Display Omitted
Keywords: Diruthenium; Heterometallic carbonates; Tetrahedral zinc; Magnetic properties;

A new mononuclear complex was successfully synthesized on the basis of a Schiff-base ligand L = 1,2-phenylendiamine-N,N′-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) and CuCl2. Its structure was characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA) and powder X-ray diffraction. The complex has a remarkable activity for photodegradation of organic dyes under visible-light illumination. Moreover, the complex showed optical property: a fluorescence quenching phenomenon was observed at 518 nm when using a 350 nm excitation light to stimulate the samples.The catalyst combined with H2O2 in the presence of visible light showed photocatalytic activity with 89% degradation of RHB after 60 min.Display Omitted
Keywords: Photodegradation organic dyes; Optical property; Schiff bases; Single crystal;

Fabrication of ZIF-8@super-macroporous poly(glycidyl methacrylate) microspheres by Xin Cao; Lin Dai; Jing Liu; Luying Wang; Jing He; Lihong Deng; Jiandu Lei (65-69).
ZIF-8@super-macroporous poly(glycidyl methacrylate) (SM-PGMA) microspheres were synthesized. The SM-PGMA microsphere was a novel material with high surface areas and large pore size. Here, ZIF-8 was loaded effectively both on the surface and inside of the macro-pores of microspheres by a facile way. The ZIF-8@SM-PGMA microspheres were characterized by SEM, TEM, XRD and FTIR. Additionally, they were used as an adsorbent material for the adsorption of phenol from aqueous solutions. The results indicated that the ZIF-8@SM-PGMA microspheres possessed apparently higher adsorption capacity for phenol than that of SM-PGMA microspheres. The ZIF-8@SM-PGMA microspheres obtained in this study have great potential for adsorption, separation, catalysis etc.ZIF-8@super-macroporous poly(glycidyl methacrylate) (SM-PGMA) microspheres were synthesized. The ZIF-8@SM-PGMA microspheres have great potential for adsorption, separation, catalysis etc.Display Omitted
Keywords: Metal–organic frameworks; Super macroporous microsphere; Adsorption; Poly(glycidyl methacrylate);

[H3O]2[{Cu6(bipy)10(H2O)4}{Cu2(bipy)2(H2O)4}{(HO2CC2H4PO3)Mo5O15(O2CC2H4PO3)}2{(HO2CC2H4PO3)2Mo5O15}2]·30H2O (1) was obtained from aqua solution. In 1 the linkage between bipy and Cu2 + ions creates a layer with rhombus channel and an isolated chain. [(HOOCC2H4PO3)2Mo5O15]4 – anions act as tridentate and tetradentate ligands, connecting the layers and the chains into a three dimensional covalent framework through the oxygen atoms of carboxylate groups and of MoO6 octahedra.In [H3O]2[{Cu6(bipy)10(H2O)4}{Cu2(bipy)2(H2O)4}{(HO2CC2H4PO3)Mo5O15(O2CC2H4PO3)}2{(HO2CC2H4PO3)2Mo5O15}2]·30H2O the linkage between bipy and Cu2 + ions creates a layer with rhombus channel paralleling to the ab plane and an isolated chain stretching along the b-axis and at the center of the rhombus channel. [(HOOCC2H4PO3)2Mo5O15]4 – anions act as tridentate and tetradentate ligand, connecting the layers and the chains into a three dimensional covalent framework through the oxygen atoms of the carboxylate groups and of MoO6 octahedra.Display Omitted
Keywords: 3-D covalent framework; Strandberg-type polyoxoanion; Organophosphonate–polyoxoanion derivatives; Copper; Phosphonocarboxylate;

A novel Eu(III)–Ag(I) coordination polymer [Eu2Ag(μ 4-oPyIDC)2(NO3)(H2O)] n (H3 oPyIDC = 2-(pyridine-3-yl)-1H-imidzole-4,5-dicarboxylate, 1) was formed based on a planar hexanuclear heterometallic Eu4Ag2 secondary building unit. The planar hexanuclear secondary building blocks are interconnected to a 3D framework with pcu topology. The luminescence property of compound 1 is also investigated.A novel Eu(III)–Ag(I) heterometallic coordination polymer based on planar hexanuclear heterometallic second building unit was constructed.Display Omitted
Keywords: Heterometallic CP; Planar hexanuclear SBU; Luminescence property;

Anion-dependent construction of three Cd(II) coordination polymers containing helical chains: Structures and luminescence properties by Zhen Zhen Wen; ShengRun Zheng; SongLiang Cai; JunGu Guo; Xuan Huang; Jun Fan; Wei-Guang Zhang (79-83).
Three new coordination polymers, [Cd(μ3-PyBIE)(NO3)]n (1), [Cd(μ2-HPyBIE)2(ClO4)2]n (2) and {[Cd1.52-HPyBIE)Cl3]·2H2O}n (3), were synthesized by the solvothermal reactions of a new benzimidazole derivative ligand, 1-(1-(pyridin-4-ylmethyl)-1H-benzoimidazol-2-yl)ethanol (HPyBIE). Crystal structure analysis showed that all the compounds were two-dimensional (2D) layer structures based on 1D helical secondary building units (SBUs). The helicity of 1D helical chain is dependent on the chiral conformation of HPyBIE ligand. Investigation of their structural diversity reveals that anions play an important role in the assembly procedure. Furthermore, the luminescence properties of compounds 13 were also studied.Three anion-dependent Cd(II) coordination polymers based on 1D helical secondary building units were constructed. The correlations among the chirality of building unit and the helicity of helical chain were investigated.Display Omitted
Keywords: Chiral; Helicity; Anion-dependent; Cd(II) coordination polymers;

A rhodamine-based optical sensor Rh–3S has been developed for selective detection of Hg2+ in aqueous solution as well as in living cells. UV–vis and fluorescence spectroscopic studies reveal that Rh–3S shows marked sensitivity and selectivity to Hg2+ with a chelation-induced “off–on” response in acetonitrile (ACN)/MOPS buffer (10 mM, pH 7.3, v/v, 1:1). The Rh–3S sensor binds Hg2+ in a 1:1 stoichiometry with an apparent binding constant 3.71 × 106  M− 1 (log K = 6.57) and displays a distinct change in color and fluorescence upon the alteration of free Hg2+ levels in solution with a reversible response and little interference with other biological relevant metal ions. Live cell confocal imaging studies demonstrate that the sensor is also capable of imaging the presence of Hg2+ ions as well as its dynamic changes in live cells.A rhodamine-based optical sensor Rh–3S has been developed for selective detection of Hg2+ in aqueous solution as well as in living cells. Live cell confocal imaging studies demonstrate that the sensor is capable of imaging the presence of Hg2+ ions as well as its dynamic changes in live cells.Display Omitted
Keywords: Fluorescence; Sensor; Rhodamine; Mercury ions; Live cell imaging;

A trans-bis(salicylaldiminato)platinum(II) complex (1) incorporating a 20-membered macrocyclic vaulting structure formed by an ethylenepenta(oxyethylene) bridge was synthesized and subsequently characterized by 1H and 13C NMR, COSY, NOESY, FT-IR, high-resolution mass spectrometry and single crystal XRD. Complex 1 in the crystalline state exhibited intense yellow emission at 298 K under UV excitation at 420 nm. The mechanistic rationale for the solid-state emission is discussed based on the molecular structure and crystal packing of this complex in comparison with those of an 11 membered, short vaulted analog (2) bearing an ethylenedi(oxyethylene) bridge.A trans-bis(salicylaldiminato)platinum(II) complex (1) bearing a 20-membered macrocyclic vaulting structure formed by an ethylenepenta(oxyethylene) bridge was synthesized and subsequently characterized by 1H and 13C NMR, COSY, NOESY, FT-IR, high-resolution mass spectrometry and single crystal XRD. Complex 1 in the crystalline state exhibited intense yellow emission at 298 K under UV excitation at 420 nm. The mechanistic rationale for the solid-state emission is discussed based on the molecular structure and crystal packing of this complex in comparison with those of an 11-membered, short vaulted analog (2) bearing an ethylenedi(oxyethylene) bridge.Display Omitted
Keywords: Platinum(II); Vaulted complex; Schiff bases; Phosphorescence;

An unusual Cd-substituted sandwich-type polyoxomolybdate cluster {Mo20Cd2} for photocatalysis of organic pollutant by Hai-Yan Liu; Guang-Hui Wang; Jin Yang; Ying-Ying Liu; Jian-Fang Ma (92-96).
An unusual Cd-substituted sandwich-type polyoxomolybdate cluster {Mo20Cd2}, namely, [Cd(H2ttb)(H2O)Mo10O32(ttb)]2·3H2O (1) has been synthesized under hydrothermal condition (ttb = 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethyl benzene). Its structure has been determined by single crystal X-ray diffraction analysis and further characterized by elemental analysis, IR and TG. In 1, two decademolybdates are functionalized by ttb organic groups, which are further linked into a sandwich-type polyoxometalate cluster {Mo20Cd2} via two [Cd(H2O)(H2ttb)]4 + cations. The solid state photoluminescent property of 1 was investigated at room temperature. In addition, its photocatalytic performance for methylene blue (MB) has also been studied under UV irradiation.An unusual Cd-substituted sandwich-type polyoxomolybdate cluster {Mo20Cd2} has been successfully synthesized under hydrothermal condition, where its photocatalytic performance for methylene blue (MB) has been studied under UV irradiation.Display Omitted
Keywords: Polyoxomolybdate; Sandwich-type structure; Luminescence; Photocatalysis;

Two new cobalt(II) coordination polymers, {[Co(OBA)(1,3-bib)]2}n·H2O (1) and [Co(OBA)(1,2-bib)]n·H2O (2), (H2OBA = 4,4′-oxydibenzoic acid; 1, 3-bib = 1,3-bis(imidazol-l-yl-methyl)benzene; 1, 2-bib = 1,2-bis(imidazol-l-yl-methyl)benzene), have been obtained by the hydrothermal reactions. Compound 1 displays a two-dimensional grid net. Compound 2 exhibits a three-dimensional porous network with 12.5% porosity. Their third-order nonlinear optical (NLO) properties were determined by Z-scan technique in DMSO solution. Two compounds show strong third-order nonlinear optical absorption and self-focusing effects with absorptive coefficients β(MKS) 8.29 × 10− 11  m·W− 1 for 1 and 6.89 × 10− 11  m·W− 1 for 2, and the refractive indexes γ(MKS) 4.37 × 10− 18  m2·W− 1 for 1 and 5.22 × 10− 18  m2·W− 1 for 2. The third-order NLO susceptibility χ(3) are calculated to be 1.86 × 10− 11 for 1, 1.58 × 10− 11 esu for 2. These values are larger than those of C60, phthalocyanine derivatives and semiconductor materials.Two cobalt(II) coordination polymers are reported. Their third-order nonlinear optical properties were determined by Z-scan technique in DMSO solution. Two compounds show strong third-order nonlinear optical absorption and self-focusing effects, and the third-order NLO susceptibility χ(3) is calculated to be 1.86 × 10− 11 for 1, 1.58 × 10− 11 esu for 2.Display Omitted
Keywords: Third-order nonlinear optics; Z-scan; Transition metal; Coordination polymer; Crystal structure;

A novel 3D self-penetrating framework self-assembled from interweaving double-helical chains by Xiao-Lin Chi; Jun-Liang Liu; Hai-Yan Chen; Juan Yang; Hua-Yi Zhang; Jin-Ling Zhang; Yu Chen; Qi Yang; Dong-Rong Xiao (101-105).
Hydrothermal reaction of the flexible V-shaped ligand 3,3,4,4-diphenylsulfone tetracarboxylic acid (H4dpstc) with nickel salt in the presence of long-chain N-donor ligand affords a fascinating entangled network, [Ni2(dpstc)(bim)2(H2O)]·2H2O (1) (bim = 1,4-bis(imidazol-1-yl)butane). Complex 1 represents an unusual 3D self-penetrating entangled framework, which is based on novel 2D helical layers. More interestingly, the 2D helical layers are constructed by the intertwined homo-axis covalent helices running along the same crystallographic 21 axis in the b direction. Furthermore, the magnetic properties of complex 1 have been studied by measuring its magnetic susceptibility in the temperature range 2–300 K.Complex 1 exhibits an unprecedented 3D self-penetrating coordination framework constructed by intertwined homo-axis covalent helices.Display Omitted
Keywords: Entangled framework; Self-penetrating; Homo-axis helices;

A two dimensional microporous metal-organic framework for selective gas separation by Hussah Alawisi; Bin Li; Khalid Alfooty; Ling Wu; Shengchang Xiang; Hailong Wang; Banglin Chen (106-109).
A new organic ligand of 1,1′-biphenyl-containing tetra-carboxylic acid (H4BPTT) and its first metal-organic framework [Zn2(BPTT)(H2O)2]n·(DMF)4.5n (1) was designed, synthesized and structurally characterized exhibiting two-dimensional distorted (4,4) topology. The activated 1a exhibits permanent porosity and moderately high selectivities for CO2/N2 and CO2/CH4 gas separations at room temperature.A new two-dimensional microporous metal-organic framework has been synthesized from a novel organic linker and structurally characterized, exhibiting moderately high selectivities for CO2/N2 and CO2/CH4 gas separations at room temperature.Display Omitted
Keywords: Metal-organic framework; X-ray crystal structure; Gas separation; Gas sorption;

Photophysical and photocatalytic behavior of cobalt(III) 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin by Melinda A. Fodor; Ottó Horváth; Lajos Fodor; Günter Grampp; Alexander Wankmüller (110-112).
Although kinetically inert cationic Co(III)TMPyP5 + (H2TMPyP4 +  = 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin) was considered earlier to be very weakly emissive, both the spectrum and the lifetime of its fluorescence could be determined. Besides, this complex proved to be favorable for outer-sphere photoinduced reduction of the metal center in the presence of triethanolamine (TEOA) as electron donor quenching the triplet excited state of this metalloporphyrin. The corresponding cobalt(II) porphyrin formed in this way was also photoactive; it forwarded an electron to a suitable acceptor (e.g., methylviologen) upon irradiation, regenerating the starting complex. Hence, this system may be a candidate for hydrogen generation from water by the utilization of visible light.Water-soluble Co(III)TMPyP5 + hyper-porphyrin displayed characteristic fluorescence and proved to be an efficient photocatalyst in a visible light-driven system containing triethanolamine and methylviologen.Display Omitted
Keywords: Cobalt(III) porphyrin; Water-soluble; Fluorescence; Photocatalysis; Triplet state;

Solvent free oxidation of sulfides to sulfones by H2O2 in the presence of chromium substituted polyoxometalate as catalyst by Roozbeh Afrasiabi; Fariba Jalilian; Bahram Yadollahi; Mostafa Riahi Farsani (113-116).
Solvent-free oxidation of sulfides into sulfones by 30% hydrogen peroxide has been achieved using chromium substituted Keggin type polyoxometalate under mild reaction conditions in 94–100% yield. This catalytic system showed excellent activity in the oxidation of sulfide groups. The other active functional groups such as hydroxyl and C=C bond have been tolerated.Chromium substituted Keggin type polyoxometalate (TBA)4[PW11CrO39]·3H2O catalyzed oxidation of various sulfides into the corresponding sulfones by hydrogen peroxide in excellent yields. Chemoselectivity, room temperature reactions and solvent free conditions are the other advantages for this catalytic system.Display Omitted
Keywords: Substituted polyoxometalate; Catalysis; Oxidation; Sulfide; Hydrogen peroxide; Solvent free;

Tris{2,4-bis(2-pyridyl)-1,3,5-triazapentanedienato}manganese(III), a complex derived from a unique metal ion-assisted transformation of pyridine-2-amidoxime by Vasilios Duros; Harikleia Sartzi; Simon J. Teat; Yiannis Sanakis; Olivier Roubeau; Spyros P. Perlepes (117-121).
A novel metal ion-mediated reaction of pyridine-2-amidoxime has led to a 1:3 mononuclear Mn(III) complex containing the 2,4-bis(2-pyridyl)-1,3,5-triazapentanedienate(− 1) ligand; the high-spin MnIII in the complex is “EPR silent” at X-band.A novel manganese-assisted transformation of pyridine-2-amidoxime has been observed, leading to a mononuclear octahedral Mn(III) complex containing the 2,4-bis(2-pyridyl)-1,3,5-triazapentanedienate(− 1) ligand.Display Omitted
Keywords: EPR spectra; Manganese(III) complex; Metal-ion-assisted ligand's transformation; Pyridine-2-amidoxime; 2,4-Bis(2-pyridyl)-1,3,5-triazapentanedienate(− 1) ligand;