Lanthanide coordination polymers for multi-color luminescence and sensing of Fe3 +

Luminescent lanthanide coordination polymers [H₂NMe₂]₃[Ln(DPA)₃] (Ln = Eu, Tb, Sm, Dy; [H₂NMe₂]⁺ = dimethyl amino cation; H₂DPA = 2,6-dipicolinic acid) are synthesized, whose multi-color can be tuned and even white color luminescence can be integrated. Besides, the fluorescent sensing property of the [H₂NMe₂]₃[Tb(DPA)₃] system is checked, which shows selective fluorescent quenching effect for Fe^3 +.     

A highly selective turn-on sensor for Hg2 + based on a phosphorescent iridium (III) complex

A highly selective phosphorescent chemosensor for Hg^2 + based on the iridium (III) complex Ir(DTBT)₂(acac) (DTBT = 2-(5-(1,2 dihydroacenaphthylen-5-yl)thiophen-2-yl)benzothiazole, acac = acetylacetone) was synthesized and characterized. Ir(DTBT)₂(acac) exhibited relatively weak fluorescenceat at about 700 nm. Ir(DTBT)₂(acac) displayed a dramatic color change from near-infrared to yellow-green with the addition of Hg^2 +. More significantly, the chemosensor performed “turn-on” phosphorescent responses toward Hg^2 +.     

A unique 3D Co(II)-MOF based on [Co6(μ3-OH)4]8 +n chains: Synthesis,crystal structure,and magnetic property

A novel metal-organic framework, [Co₆(μ₃-OH)₄(ndc)₄(bip)₂(H₂O)₂]_n (1)[H₂ ndc = 1,4-naphthalenedicarboxylic acid, bip = 1,5-bis(imidazole-1-yl)pentane], constructed from unique [Co₆(μ₃-OH)₄]^8 +_n chains containing alternate [Co₄(OH)₂]^6 + and [Co₂(OH)₂]^2 + subunits, was reported, which has a new (3,3,8,12)-connected or 12-connented fcu/cubic network and shows weak antiferromagnetic interaction between the adjacent Co(II) ions mediated through the carboxylate and hydroxyl groups.     

First example of PMMA-supported and highly luminous color-purity red-light metallopolymer based on a tris-β-diketonate Zn2 +-Eu3 +-complex

Through the copolymerization of a complex monomer [Zn(L)(4-vinyl-Py)Eu(TTA)₃] (2; H₂L = N,N′-bis(salicylidene)cyclohexane-1.2-diamine; 4-vinyl-Py = 4-vinyl-pyridine and HTTA = 2-thenoyltrifluoroacetonate) with MMA (methyl methacrylate), the first example of PMMA-supported and highly luminous (Ф_Eu^L = 63.1%) color-purity red-light metallopolymer poly(MMA-co-2) based on a tris-β-diketonate Zn^2 +-Eu^3 +-complex is obtained.     

Six isostructural lanthanide-containing MOFs built on a semi-rigid tripodal organic ligand

By using a semi-rigid tripodal ligand 1,1′,1′′-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tripyridinium-4-olate) (L), six isomorphous lanthanum metal-organic frameworks (MOFs), namely, [Pr(L)₂(Cl)₂]·(Cl)(DMF)_0.5·(H₂O)·(1), [Nd(L)₂(Cl)₂]·(Cl)(2), [Tb(L)₂(Cl)₂]·(Cl)·(DMF)·(H₂O)(3), [Eu(L)₂(Cl)₂]·(Cl)(DMF)·(H₂O)(4), [La(L)₂(Cl)₂]·(Cl)(5), [Sm(L)₂(Cl)₂]·(Cl) (DMF)·(H₂O) (6), were obtained and characterized by single crystal X-ray diffraction, IR and elemental analysis. Six compounds are isostructural with Ln^3 + (Ln = Pr, Nd, Tb, Eu, La, Sm) and in which the Ln^3 + is considered as a 6-connecting node and the L ligand is a 3-connecting node to afford a (3,6)-connected 2D layer with kgd topology, which further stacks into 3D supramolecular networks through C-H^…O weak interactions. Luminescent properties of these lanthanide MOFs have also been assessed at ambient temperature, in which the Pr^3 +-1 and the La^3 +-5 are slightly blue-shifted with respect to the ligand. Series of sharp peaks characteristic of the Eu^3 +-4, the Tb^3 +-3 and Sm^3 + − 6 metal-centered luminescence appear. The Nd^3 +-2 has no emission.     

Syntheses,structures and properties of two copper-2-picolinic-acid germanomolybdate hybrids with mixed organic components

Two inorganic–organic hybrids based on saturated α-Keggin-type germanomolybdates with mixed organic components [H₂DAP]₂[Cu(PA)₂][α-GeMo₁₂O₄₀]·8H₂O (1) and [NH₄]₂[H₈L] [Cu(PA)₂][α-GeMo₁₂O₄₀]·8H₂O (2) (DAP = 1.2-diaminopropane, HPA = 2-picolinic acid, H₆L = 1,3-bis[tris(hydroxymethyl)methylamino]propane) have been obtained via the conventional aqueous solution method and structurally characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. 1 stands for an one-dimensional linear organic–inorganic hybrid germanomolybdate chain constructed from classical Keggin [α-GeMo₁₂O₄₀]^4 − units supported by [Cu(PA)₂] linkers, whereas 2 represents the first hybrid germanomolybdate containing the H₆L component and consists of a saturated α-Keggin polyanion [α-GeMo₁₂O₄₀]^4 −, a diprotonated [H₈L]^2 + cation, a copper coordination complex [Cu(PA)₂], two ammonium cations [NH₄]⁺ and eight lattice water molecules. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have also been investigated in detail.     

Catalytic hydroboration of vinylarenes using a zwitterionic arylspiroboronate ester iridium complex

Addition of B₂cat₃ (cat = 1,2-O₂C₆H₄) to Ir(acac)(dppb) (1; where dppb = 1,4-bis(diphenylphosphino)butane) gave the novel arylspiroboronate ester iridium complex Ir(η⁶-catBcat)(dppb) (2), the first example of an iridium compound containing a coordinating [Bcat₂]^? anion. Complex 2 is a remarkably selective catalyst precursor for the hydroboration of unhindered vinylarenes using pinacolborane.     

Syntheses,structural characterization and electrochemical properties of two rare-earth–isonicotinic-acid containing silicomolybdates

Two rare-earth–isonicotinic-acid containing silicomolybdates [NH₄]₆[RE(INA)₂(HINA)(H₂O)₃]₂[α-SiMo₁₂O₄₀]₂·6H₂O [RE = Nd^III (1), Er^III (2); HINA = isonicotinic acid] have been synthesized in the conventional aqueous solution and characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic P–1 space group and consist of two typical Keggin [α-SiMo₁₂O₄₀]^4 − polyanions, one isolated rare-earth-isonicotinic-acid [RE(INA)₂(HINA)(H₂O)₃]₂^2 + dimeric complex cation, six NH₄⁺ ions and six lattice water molecules. Interestingly, two rare-earth ions are linked by four INA⁻ ligands in the [Ln(INA)₂(HINA)(H₂O)₃]₂^2 + complex cation, which is very rare in polyoxometalate chemistry. The UV spectral measurements of 1 indicate that 1 is stable in aqueous solution in the pH range of 4.49–9.39. Furthermore, the electrochemical and electrocatalytic properties of 1 have been measured by cyclic voltammetry in 0.5 mol·L^− 1 Na₂SO₄ + H₂SO₄ aqueous solution at the scan rate of 100 mV·s^− 1.     

A hybrid microreactor/microwave high-pressure flow system of a novel concept design and its application to the synthesis of silver nanoparticles

This article reports on a microreactor/microwave high-pressure flow hybrid apparatus of a novel concept design, which includes both the microreactor and a spiral reactor, and its efficient use in the synthesis of silver nanoparticles of relatively uniform sizes (4.3 ± 0.7 nm) under microwave irradiation. By contrast, under otherwise identical experimental conditions but with conventional heating, the nanoparticle size was non-uniform (8.3 ± 2.7 nm) and the spiral reactor walls were covered with a silver mirror deposit. Formation of the nanoparticles was monitored by UV–visible spectroscopy (plasmonic absorption band; LSPR), TEM and by small-angle X-ray scattering (SAXS). Both the spiral microreactor and the spiral quartz reactor of the hybrid system played an important role in the synthesis, with the microreactor providing the environment wherein mixing of the aqueous solution of [Ag(NH₃)₂]⁺ and the solution of glucose (the reducing agent) and poly(N-vinyl-2-pyrrolidone) (PVP; stabilizer/dispersing agent) occurred. The microwaves provided the thermal energy to effect a uniform growth of the silver nanoparticles at temperatures above 120 °C. Mixing the two solutions by conventional methods (no microreactor) failed to yield such nanoparticles even under microwave irradiation and no formation of a silver mirror occurred in the inner walls of the spiral reactor.     

One 2D anionic coordination polymer with {[Co(H2O)6]}2 + cationic guest for fast and selective adsorption of cationic dyes

One new anionic Coordination Polymer, namely [Co(H₂O)₆]^2 +·[Co₃(bptc)₂(H₂O)₁₀]^2 −·3H₂O (1), where H₄bptc = 3,3′,5,5′-biphenyltetracarboxylate, has been synthesized hydrothermally and characterized. In compound 1, bptc^4 − as tridentate ligands connect the Co^2 + cations to form a 2D layer with 1D pseudo channels encapsulation of [Co(H₂O)₆]^2 + guest. In addition, their adsorption activities for organic dyes were investigated in aqueous solution. The results suggested that the anionic complex 1 show rapid and selective adsorption of cationic dyes for Neutral red, Methylene blue.     

A luminescent europium metal–organic framework with free phenanthroline sites for highly selective and sensitive sensing of Cu2 + in aqueous solution

A luminescent europium metal–organic framework [Eu(HL)(L)(H₂O)₂]·2H₂O (1) (H₂L = (2,3-f)-pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid) with uncoordinated phenanthroline nitrogen sites was hydrothermally synthesized. It exhibits highly sensitive and selective sensing of Cu^2 + in aqueous solution. To the best of our knowledge, complex 1 is the first luminescent Eu-MOF with uncoordinated phenanthroline nitrogen sites for selective sensing of Cu^2 + in aqueous solution. The probable sensing mechanism was discussed in detail.     

Construction and structural diversity of Cd-MOFs with pyrazole based flexible ligands and positional isomer of naphthalenedisulfonate

In the present communication, we have reported the construction of a series of Cd(II)-MOFs using conformationally flexible ligand (CFL); 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl (H₂BPz), flexible bent ligand (FBL); methylenebis-(3,5-dimethylpyrazole) (H₂MBPz) and positional isomer of naphthalene disulfonic acid salt ligands (1,5-NDS, 2,6-NDS). By using these ligands, four new coordination polymers namely [Cd(H₂MBPz)₂∙ 1,5-NDSA]_n (NDS-MOF-1), [Cd(H₂BPz)∙ 1,5-NDSA]_n (NDS-MOF-2), {[Cd(H₂MBPz)₂]^2 +∙ 2,6-NDSA^2 −}_n (NDS-MOF-3) and {[Cd(H₂BPz)₂]^2 +∙ 2,6-NDSA^2 −}_n (NDS-MOF-4) have been synthesized. The crystal structure analysis revealed that the employment of positional isomeric naphthalene disulfonic acid salts resulted in different architectures ranging from one dimensional chain to two dimensional grid network and further connected into a three dimensional supramolecular structure through intermolecular hydrogen bonds, π⋯π and C–H⋯π interactions. In addition, the photophysical properties and thermal stability studies for all the NDS-MOFs 1–4 were also investigated.     

Synthesis,structural characterization and properties of a novel 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O

An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)₂][Cu(en)(H₂O)][(Cu(en)₂(H₂O)] [As^IIIAs^VMo₉O₃₄)]} · 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 [As^IIIAs^VMo₉O₃₄]^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)][As^IIIAs^VMo₉O₃₄)]}^2 − clusters and [Cu(en)₂]^2 + linkers.     

The spin gap system by self-assembly of benzyl-4-ethylpyridinium and bis(maleonitriledithiolate)niclelate(III) anion

The self-assembly of [BzEtPy]⁺([BzEtPy]⁺ = benzyl-4-ethylpyridinium) cation and the [Ni(mnt)₂]^? (mnt^2? = maleonitriledithiolate) anion results in the forming of a new molecular solid [BzEtPy][Ni(mnt)₂](1), in which the anions and cations stack into columns and the Ni(III) ions form a 1D zigzag alternating chain through Ni···S and π···π interactions between [Ni(mnt)₂]^? anions with the Ni···Ni distances of 3.886 Å and 4.781 Å, and the four columns of cations create cubic-like large channel in which the [Ni(mnt)₂]^? columns are located. Magnetic susceptibility measurements show that 1 exhibits a spin gap transition around 90 K.     

An unprecedented mixed valence cobalt(III)/cobalt(II) ion-pair complex ([CoCO3(bipy)2]2[Co(DCA)2]⋅16H2O) with two novel water tapes

An unprecedented mixed valence cobalt(III)/cobalt(II) ion-pair complex, [CoCO₃(bipy)₂]₂[Co(DCA)₂]⋅16H₂O (1) [bipy = 2,2′-bipyridine, DCA = demethylcantharidate, exo-1,4-epoxy-cyclohexyl-2,3-dicarboxylate group, (C₈H₈O₅)^2 −], has been synthesized and characterized by elemental analysis, IR, UV–vis, Thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The crystal structure of 1 consists of three independent molecular moieties: [CoCO₃(bipy)₂]⁺, [Co(DCA)₂]^2–, and water molecules of crystallization. Interestingly, two novel water tapes, one comprises of alternate cyclic water tetramer and octamer, the other is constructed by alternate cyclic water hexamer and carboxylate–water hybrid octamer [(H₂O)₂(COO)₂]^2 −, have been detected for the first time in the host framework of 1. The two novel water tapes are linked together by the DCA and carbonate ligands via hydrogen bonds into a 2D water layer, and then the water layers assemble complex ions ([CoCO₃(bipy)₂]⁺ and [Co(DCA)₂]^2 −) through hydrogen bonds, π–π interactions and electrostatic interactions to form the overall 3D metal–organic framework structure.     

Formation of RuO2 nanoparticles by thermal decomposition of Ru(NO)(NO3)3

A simple one-pot synthesis of RuO₂ nanoparticles by the thermal decomposition of ruthenium nitrosyl nitrate [Ru(NO)(NO₃)₃] up to 800 °C was investigated. The RuO₂ phase was characterized by XRD, SAXS, FE SEM/EDS, Raman, DTA/TGA and FT-IR techniques. Broadening of prominent diffraction lines (110), (101) and (211) was used to estimate nanocrystallite sizes in RuO₂ particles. FE SEM showed the formation of RuO₂ plates at 400 °C which consisted of RuO₂ nanoparticles of about 15–25 nm in size. At 800 °C RuO₂ nanoparticles showed the sintering effect and some of them increased in size to about 200 nm. Raman and FT-IR spectra consolidated the findings. Moreover, DTA curves showed the decomposition and release of NO and NO₃⁻ groups to be a stepwise process.     

Role of vermiculite and zirconium–vermiculite on the formation of zircon–cordierite nanocomposites

The Zr^4 +–vermiculites were studied in their new role of the zircon precursor in the clay minerals mixtures which were prepared for firing of the zircon–cordierite nanocomposites. Currently there is a lack of data available about the structure of Zr^4 +–vermiculites, on which this study was performed. The modeling of the arrangement of interlayer material in the Zr^4 +–vermiculite led to new findings that water molecules are attracted more strongly by Mg^2 + cations than by Zr-tetrameric cations, and that both the tetrameric cations [Zr₄(OH)₁₄(H₂O)₁₀]^2 + and [Zr₄(OH)₈(H₂O)₁₆]^8 + may be present in the interlayer space of the Zr^4 +–vermiculites. Vermiculites from two different localities Czech Republic (Verm1) and from Brazil (Verm2) were intercalated using the zirconyl chloride (ZrOCl₂–30% solution in HCl) and the prepared Zr^4 +–vermiculites were designated as Zr^4 +–Verm1 and Zr^4 +–Verm2, respectively. Influence of the Zr^4 +–Verm1 and Zr^4 +–Verm2 in the mixtures of clay minerals on the properties of zircon–cordierite nanocomposites were investigated by their comparison with the properties of the zircon–cordierite nanocomposites, which were prepared using saturation of the clay minerals mixtures containing Verm1 and Verm2 with the zirconyl chloride (ZrOCl₂–30% solution in HCl). The zircon–cordierite nanocomposites fired from the clay mineral mixtures containing Zr^4 +–Verm1 and Zr^4 +–Verm2 showed a maximum porosity of P = 58 and 60%, skeletal density SD = 3.2 and 3.6, and the smallest pores with a median pores diameter MDP = 18 and 15 μm, respectively, in comparison with the zircon–cordierite nanocomposites fired from the clay mineral mixtures containing Verm1 and Verm2 and saturated with zirconyl chloride solution. The type of vermiculite Verm1 or Verm2 in the clay mineral mixtures did not affect the contents of the crystalline mineral phases in cordierite and zircon–cordierite nanocomposites.     

Three novel bismuth-based coordination polymers: Synthesis,structure and luminescent properties

Three novel bismuth-based coordination polymers, [(CH₃)₂NH₂][Bi(pdc)(bdc)]·2DMF, [(CH₃)₂NH₂][Bi(tdc)₂]·1.5DMF and [Bi(bpdc)₂H₂O]·xGuest (compounds 1–3) (H₂pdc = 3,5-pyridinedicarboxylic acid, H₂bdc = 1,4-benzenedicarboxylic acid, H₂tdc = 2,5-thiophenedicarboxylic acid, H₂bpdc = 4,4′-biphenyldicarboxylic acid), have been successfully synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction. Compounds 1 and 2, which are constructed by 9-coordinated or 8-coordinated Bi^3 +, feature three-dimensional structures with hms and dia topology, respectively. However, 5-coordinated Bi^3 + based compound 3 is a two-dimensional layered structure. Compound 1 can tune emissive performance by doping different lanthanide ions Tb^3 +, Eu^3 + and Dy^3 +. Furthermore, detection of nitro explosives is investigated. All of the compounds are characterized by elemental analysis, IR spectrum and thermogravimetric analysis.     

A study on proton conduction in a layered metal–organic framework,Rb2(adp)[Zn2(ox)3]·3H2O (adp = adipic acid,ox2 − = oxalate)

We newly synthesized a metal–organic framework (MOF) Rb₂(adp)[Zn₂(ox)₃]·3H₂O (adp = adipic acid; ox^2 − = oxalate), where the rubidium ions, carboxylic acid groups, and water molecules are located in an interlayer space of a two-dimensional (2-D) oxalate-bridged network. The structure of this compound was determined using single-crystal X-ray diffraction analysis. Hydrated phases of this compound were examined using thermogravimetry and water vapor adsorption measurements. Proton conductivity in this MOF was investigated by alternating current impedance measurements. Systematic comparison with previously reported isomorphous 2-D compounds A₂(adp)[Zn₂(ox)₃]·3H₂O (A = NH₄ and K) showed that the difference in the ionic radii of the cations leads to a difference in activation energy of proton conductivity and that absence of NH₄⁺ ions causes a significant decrease in proton conductivity, even though the ionic radius of Rb⁺ (1.52 Å) is closer to that of NH₄⁺ (1.61 Å) than that of K⁺ (1.38 Å).     

A new stable Cd(II)-framework for sensitive and selective detection of Cu2 + ions

A new water-stable 3D metal–organic framework (MOF), [Cd₂L₂]·NMP·MeOH (1, H₂L = 2-(3,5-dimethyl-1H-pyrazol-4-yl)-1,3-dioxoisoindoline-5,6-dicarboxylic acid, NMP = 1-methyl-2-pyrrolidinone) has been solvothermally synthesized and structurally characterized. 1 exhibits a 3D open-framework with a 2D metallic plane pillared by L^2 − fragments. Meanwhile, luminescent studies indicate that the luminescence intensity of 1 was strongly dependent on different metal ions. Most interestingly, 1 exhibited significantly quenching effect toward Cu^2 +, which implies that it may be used as a luminescent probe for the detection of Cu^2 +.