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At least 991 records · Page 55

Large-Area Lasing in Nanoscale Complex Media: The Critical Role of Local Dielectric Environment

Controlling how electromagnetic waves interact with complex media is critical for applications in imaging and focusing. Such lightwave interactions with complex media can lead to dramatic optical effects like lasing. While much work in random lasing focus on understanding how gain and scattering co-operatively generate lasing, little work has focused on how to manipulate the lasing threshold without modifying the structural disorder. Here, a simple, mostly unexplored, strategy is demonstrated that employs atomic layer deposition (ALD) to tune the local near-field environment while preserving the underpinning disorder—controlling lasing in a nanoscale complex medium on a large scale (>cm 2 ). The nanoscale complex medium is a quasi-2D system of coupled zinc oxide nanospheres with overall thickness deep in the sub-wavelength regime (≈λ/4). Near-ultraviolet femtosecond spectroscopy probes the broadband response of the gain nanomaterial, details how ALD process fundamentally modifies the fast-picosecond and slow-nanosecond carrier dynamics, and informs on the relevant timescales critical for lasing. Full-field electromagnetic simulations provide critical insights about how near-field dielectric environment modifies the nanostructure's scattering cross-section, which ultimately results in enhanced lasing. Importantly, these results highlight a simple path to control how electromagnetic waves interact in a complex medium, a key step toward large-scale implementation of complex lasers.

36 MATERIALS SCIENCE↗

Characterization of Ce SUP 3+-tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary

Coordination complexes containing Ce(III) and tri-n-butyl phosphate (TBP) in the 1+, 2+ and 3+ charge states were generated using desorption electrospray ionization (DESI) mass spectrometry, in which the analyte solutions were supplied via a target capillary orthogonally situated with respect to the electrospray. Comparison with direct electrospray (ESI) showed that the same coordination complexes were produced in each experiment, and could be described by the general formula [Ce(NO3)m=0-2(TBP)n](3-m)+. This result indicates that DESI has utility for measuring metal speciation for metal ligand solutions where the gas-phase complexes generated by ESI have been correlated with solution speciation. Such an application would be useful for analyses where it is desirable to limit the total amount of metal being handled, or that have solvent systems that are not readily amenable to ESI. Both the direct ESI and DESI mass spectra showed similar trends with respect to the TBP:Ce ratio, viz. high values tend to favor formation of a larger fraction of the 1+ species, and the 2+ and 3+ species become relatively more important as the ratio is decreased. Within individual charge state ion envelopes, lower TBP:Ce ratios produce coordination complexes with fewer ligands, a trend also seen using both approaches. These trends again point toward strong similarity between the direct ESI and DESI analyses of the metal-ligand solutions. The DESI experiments were less sensitive for measuring the coordination complexes compared to the direct ESI experiments, by a factor of 10 - 100 depending on whether minimum detectable concentration or absolute ion abundances were considered. Nevertheless, mid-picomolar quantities of coordination complexes were measured using the target capillary, indicating that sensitivity would be sufficient for measuring species in many industrial separations processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of Quantum States Based on Creation Complexity

Abstract The creation complexity of a quantum state is the minimum number of elementary gates required to create it from a basic initial state. The creation complexity of quantum states is closely related to the complexity of quantum circuits, which is crucial in developing efficient quantum algorithms that can outperform classical algorithms. A major question unanswered so far is what quantum states can be created with a number of elementary gates that scales polynomially with the number of qubits. In this work, it is first shown that for an entirely general quantum state it is exponentially hard (requires a number of steps that scales exponentially with the number of qubits) to determine if the creation complexity is polynomial. Then, it is shown that it is possible for a large class of quantum states with polynomial creation complexity to have common coefficient features such that, given any candidate quantum state, an efficient coefficient sampling procedure can be designed to determine if the state belongs to the class or not with arbitrarily high success probability. Consequently, partial knowledge of a quantum state's creation complexity is obtained, which can be useful for designing quantum circuits and algorithms involving such a state.

74 ATOMIC AND MOLECULAR PHYSICS↗

Mercury Complexation with Dissolved Organic Matter Released from Thirty-Six Types of Biochar

Previous studies show mercury (Hg) can be effectively removed from solution by biochar, but limited attention was paid on the complexation between Hg and components released from biochars, e.g. dissolved organic matter (DOM). Here, aqueous data from batch-style experiments were modeled using PHREEQC, incorporating thermodynamic constants between Hg and DOM, which was assumed to be composed of thiol, carboxylic, and phenolic functional groups. Modelling results suggest that > 99% Hg complexed with thiol groups in DOM. The modelled concentrations of Hg–DOM complexes from low-T (low-temperature, 300°C) biochars were greater than from high-T (600°C) biochars. The concentrations of Hg–DOM complexes were lower in wood-based than in agricultural residue- and manure-based biochars. Hg–DOM complexes may affect Hg speciation, bioavailability, transport, and methylation processes. This research describes a method to evaluate Hg–DOM interactions, and the results indicate extra caution regarding Hg–DOM complex formation is required in the selection of biochar for Hg remediation.

54 ENVIRONMENTAL SCIENCES↗

Dichlorosilylene–hydrogen chloride complex: direct IR spectroscopic detection in argon matrix

A 1: 1 donor–acceptor complex between SiCl{sub 2} and HCl was detected by matrix IR spectroscopy. The existence of the complex was previously predicted theoretically in the course of analysis of mechanisms of chemical vapor deposition (CVD) processes involving chlorosilanes. The quantum chemical calculations at the G4(MP{sub 2}) level confirmed the possibility of formation of only one stable complex upon the reaction of SiCl{sub 2} with HCl. In addition to the complex of the simplest composition, complexes of SiCl{sub 2} with HCl associates were observed upon matrix annealing. The only product formed upon the photolysis of the complexes of all types was trichlorosilane, a product of silylene insertion into the H–Cl bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer nanoparticles of N-vinylpyrrolidone loaded with an organic aminonitroxyl platinum (IV) complex. Characterization and investigation of their in vitro cytotoxicity

The conditions for obtaining stable aqueous solutions of a lipophilic aminonitroxyl platinum complex, namely, e-amine-d-(4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl)-a, f-bis(octanoato)-b, c-dichloroplatinum(IV), by means of its encapsulation into nanoparticles of copolymers of N-vinylpyrrolidone with triethylene glycol dimethacrylate with various monomer compositions and topologies were found. Aqueous solutions of the complex encapsulated into polymer particles were investigated by dynamic light scattering, the temperature dependence of nanostructure sizes was studied. Transmission electron microscopy established that the hybrid nanostructures are core—shell particles, in which the platinum complex forms small clusters (∼4 nm). The parameters of ESR spectra of aqueous dispersions indicate a high mobility of nitroxyl contained in hybrid nanostructures. Voltammetric measurements demonstrate a similarity of the redox reactions related to the free radical fragment of the aminonitroxyl Pt{sup IV} complex and of the 4-acetylamino-2,2,6,6-tetramethylpiperidine 1-oxyl radical. Polymer products containing the platinum complex were studied by IR spectroscopy, TGA, and DSC. The cytotoxicity index (IC{sub 50}) of the free and the encapsulated complex was determined for HeLa tumor cells. The cytotoxicity of the latter (IC{sub 50} 47–205 nmol L{sup −1}) depends on the monomeric composition of the nanoparticles and the incubation time.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Copper complexes: cytotoxicity and transport possibilities

A copper complex with N-(5,6-dihydro-4H-1,3-thiazin-2-yl)benzamide was synthesized for the first time and characterized by {sup 1}H NMR spectroscopy, LETDY mass spectrometry, and elemental analysis. A comparative study of the obtained complex and copper 2-aminopyrimidine complex was performed by flow cytometry on normal lymphocytes and Jurkat cells. Complexes with radionuclides {sup 64,67}Cu (with and wihout a carrier) were prepared, and distribution of the labeled complexes in the organs of mice was considered. Packing in carboxymethylcellulose-based microgels was proposed as a transport form for the complexes. The results show a promise of the obtained materials as potential radiopharmaceutical agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cryo-EM Structures Reveal Mechanism and Inhibition of DNA Targeting by a CRISPR-Cas Surveillance Complex

Prokaryotic cells possess CRISPR-mediated adaptive immune systems that protect them from foreign genetic elements, such as invading viruses. Here, a central element of this immune system is an RNA-guided surveillance complex capable of targeting non-self DNA or RNA for degradation in a sequence- and site-specific manner analogous to RNA interference. Although the complexes display considerable diversity in their composition and architecture, many basic mechanisms underlying target recognition and cleavage are highly conserved. Using cryoelectron microscopy (cryo-EM), we show that the binding of target double-stranded DNA (dsDNA) to a type I-F CRISPR system yersinia (Csy) surveillance complex leads to large quaternary and tertiary structural changes in the complex that are likely necessary in the pathway leading to target dsDNA degradation by a trans-acting helicase-nuclease. Comparison of the structure of the surveillance complex before and after dsDNA binding, or in complex with three virally encoded anti-CRISPR suppressors that inhibit dsDNA binding, reveals mechanistic details underlying target recognition and inhibition.

59 BASIC BIOLOGICAL SCIENCES↗

Synergistic foam stabilization and transport improvement in simulated fractures with polyelectrolyte complex nanoparticles: Microscale observation using laser etched glass micromodels

Inaccessibility to direct pore scale observation in hydrocarbon recovery of tight shale formations poses a great challenge to water-energy nexus initiatives and necessitates the use of high throughput technologies to emulate environmentally friendly processes. Herein, we employ a precise glass micromodel fabrication and visualization method to isolate the supercritical CO 2 bubbles surrounded by CO 2 -water lamella prepared in saline produced water stabilized with molecular complexation of zwitterionic surfactants (ZS) and polyelectrolyte complex nanoparticles (PECNP). The Selective Laser Enhanced Etching (SLE) technique was selected for micromodel simulation of high-pressure flow. Two representative designs, (1) fracture/micro-crack network 28 and (2) fracture/matrix were etched on fused silica glass with a laser printing machine and scCO 2 foam was injected to study the foamability, propagation, stability, and fluid loss properties. The highly monodispersed and uniformly distributed array of scCO 2 bubbles were detected in flow of scCO 2 foam in highly saline brine containing ionic complexes of positively charged PECNPs and ZS, whereas foam flow with the lamella containing ZS in fractures offered a noticeably large and polydisperse array of scCO 2 bubbles. scCO 2 bubble motion and deformation were traced, and local description of foam flow was visually examined. The confined array of scCO 2 bubbles stabilized by ZS in microcracks was affected by bubble growth and coalescence, whereas the super-populated array of monodispersed scC O2 bubbles with lamella containing complexes of PECNP and ZS were able to fill the channels with stable configurations within the timeframe of comparative stability measurements. The ability of complex fluid to prevent the formation damage was evaluated through fluid loss visualization in micromodels. Probing scCO 2 foam transport in homogenous porous media revealed smaller volume leak-off for scCO 2 foam containing PECNP-ZS ionic complexes.

04 OIL SHALES AND TAR SANDS↗

Complex coacervation of poly(ethylene-imine)/polypeptide aqueous solutions: Thermodynamic and rheological characterization

This study is aimed at understanding the complex coacervation of two systems: branched poly(ethyleneimine) with linear poly(D,L-glutamic acid) or poly(D,L-aspartic acid), and identify differences and similarities with previously reported systems. Three different techniques (turbidity, isothermal titration microcalorimetry-ITC and rheology) were used in a comprehensive study of coacervation. Sample turbidity was used to show how various parameters (salt, stoichiometry, pH, temperature) affect complex coacervation. Complex coacervation decreases with increase in salt and coacervate formation is maximum when a 31:69 mol% acid:base ratio is used. Rare in literature phase diagrams revealed that coacervates are formed over a wide range of acid:base ratios (15-88 mol% NH3+ groups), significantly broader compared to other systems. ITC was used for the thermodynamic characterization of the complexation between the polyelectrolytes, and showed that complex coacervation is entropy-driven (from the release of counter-ions) and enthalpically unfavored process. Composition and viscoelastic properties of the complex coacervates were examined gravimetrically and through rheology. Coacervate water content depends on the salt concentration and the stoichiometry. Coacervates exhibit a viscoelastic behavior that is dependent on the salt concentration. Master curves that can predict behavior at a wide range of time scales, not accessible by conventional rheological measurements, were created.

Complex coacervation↗

Evaluating three evapotranspiration estimates from model of different complexity over China using the ILAMB benchmarking system

The land surface models range in complexity of terrestrial evapotranspiration, yet it is unknown how model complexity translates to accuracy of modeled evapotranspiration estimates. Here, we use the International Land Model Benchmarking system to assess ET estimates from three models of varying complexity driven by the same forcing datasets: an earth system model, a terrestrial biosphere model, and a stand-alone ET model. The performance assessment includes both temporal and spatial evaluation, and different plant functional types across China. Our results indicate that the most complex model, an earth system model, performed best against the benchmarking datasets and metrics. Terrestrial biosphere model performed best in simulating inter-annual variability of ET, while earth system model performed best in simulating the seasonal cycle. The more complex models (earth system model and terrestrial biosphere model) perform better in forest, shrub and crop ecosystems, while the simpler model (stand-alone ET model) perform better in grass ecosystems. Our study demonstrates the impact of model complexity on ET estimates and highlights directions for future ET model improvements.

54 ENVIRONMENTAL SCIENCES↗

Three tetranuclear copper(II) cluster-based complexes constructed from 4-amino-1,2,4-triazole and different aromatic carboxylates: Assembly, structures, electrochemical and magnetic properties

Three new tetranuclear copper(II) cluster-based complexes constructed from 4-amino-1,2,4-triazole (atrz) and three types of aromatic carboxylates, [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(DNBA){sub 6}] (1), [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(1,3-BDC){sub 3}]{center_dot}2H{sub 2}O (2) and [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(SIP){sub 2}]{center_dot}4H{sub 2}O (3) (HDNBA=3,5-dinitrobenzoic acid, 1,3-H{sub 2}BDC=1,3-benzenedicarboxylic acid and NaH{sub 2}SIP=sodium 5-sulfoisophthalate), have been hydrothermally synthesized and structurally characterized. Complex 1 displays a single-molecular Cu{sup II}{sub 4} cluster structure, which is further connected by the intermolecular hydrogen-bonding interactions to form a 2D supramolecular layer. In 2, there also exist tetranuclear Cu{sup II}{sub 4} clusters, which are linked by the 1,3-BDC anions to give a 3D NaCl-type framework. In 3, the Cu{sup II}{sub 4} clusters are connected by the carboxyl and sulfo groups of SIP anions to generate 3D (4,8)-connected framework with a (4{sup 10}{center_dot}6{sup 14}{center_dot}8{sup 4})(4{sup 5}{center_dot}6){sub 2} topology. The atrz ligand conduces to the construction of tetranuclear copper(II) clusters and the carboxylates with different non-carboxyl substituent show important effects on the final structures of the title complexes. The electrochemical and magnetic properties of 1-3 have been investigated. - Graphical abstract: Three tetranuclear copper(II) cluster-based complexes based on different carboxylates have been synthesized under hydrothermal conditions. The carboxylate anions play a key role in the formation of three different structures. Highlights: Black-Right-Pointing-Pointer Three new tetranuclear copper(II) cluster-based complexes have been obtained. Black-Right-Pointing-Pointer The atrz conduces to the construction of tetranuclear copper(II) clusters. Black-Right-Pointing-Pointer Carboxylates show important effect on the structures of title complexes. Black-Right-Pointing-Pointer Magnetic properties and electrochemical behaviors have been reported.

36 MATERIALS SCIENCE↗

Syntheses and characterizations of two new energetic copper–amine-DNANT complexes and their effects on thermal decomposition of RDX

Two novel copper complexes of dinitroacetonitrile (DNANT), Cu(NH{sub 3}){sub 4}(DNANT){sub 2} (1) and Cu(en){sub 2}(DNATN){sub 2} (2), have been synthesized for the first time through an unique reaction, and structurally characterized. The single-crystal X-ray structural analysis shows that the Cu{sup 2+} cations in the two complexes share a similar four-coordinated structure, which however does not directly involve the main energetic DNANT{sup −} anion. The differential scanning calorimetry (DSC) study reveals that the two complexes have higher thermal stability and lower sensitivity than the analogous FOX-7 complexes, and exhibit good catalytic action to the decomposition of RDX. - Graphical abstract: Cu(NH{sub 3}){sub 4}(DNANT){sub 2} (1) and Cu(en){sub 2}(DNATN){sub 2} (2) have been first synthesized through an unique reaction. Cu{sup 2+} ion shares a similar four-coordinated structure in the two complexes. Display Omitted - Highlights: • A new reaction is unexpectedly found, and reaction process was discussed in this work. • Cu(NH{sub 3}){sub 4} (DNANT){sub 2}and Cu(en){sub 2}(DNATN){sub 2} were first synthesized through an unique reaction. • The structures and properties of the two complexes were discussed in detail, and they all present good application performances. • The adjacent amino-hydrazino group in AHDNE exhibits high reactivity. The work is another typical example for the reactivity.

36 MATERIALS SCIENCE↗

A new coordination mode of (E)-3-(3-hydroxyl-phenyl)-acrylic acid in copper complex: Crystal structure and magnetic properties

A copper complex ([Cu(py){sub 2}(L){sub 2}]·2CH{sub 3}OH){sub n} (HL=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) (1) with acrylic acid ligand was synthesized and structurally analyzed by IR, elemental analysis, TGA and the single-crystal X-ray diffraction methods. It is the first time to find that phenolic hydroxyl of L coordinates to Cu(II). Complex 1 exhibits 1D chain by a double-bridge of ligands, and the 3D supramolecular framework in complex 1 is constructed by π–π stacking interactions and van der Waals Contacts among the 1D chains. The magnetic properties of complex 1 have been studied. - Graphical abstract: A copper complex based on (E)-3-(3-hydroxyl-phenyl)-acrylic acid in a novel coordinated way was synthesized and a ferromagnetic exchange interactions between neighboring Cu(II) ions has be achieved. - Highlights: • A new copper complex with acrylic acid ligand was synthesized and analyzed. • We find the phenolic hydroxyl of MCA ligand coordinates to metal ion firstly. • A ferromagnetic exchange interactions between Cu(II) ions has been achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid

With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H{sub 2}phb) or terephthalic acid (H{sub 2}tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO{sub 2}){sub 2}(Hphb){sub 2}(phb)(DMF)(H{sub 2}O){sub 3}]·4H{sub 2}O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a µ{sub 2}-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO{sub 2})(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with µ{sub 4}-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C–O–U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated. - Graphical abstract: With the coordination of dimethylformamide, two new uranyl complexes with either 4-hydroxybenzoate or terephthalate have been synthesized under solvothermal conditions and structurally characterized. - Highlights: • Solvent facilitates the synthesis of two new uranium(VI) complexes. • A dinuclear complex with both penta- and hexagonal bipyramidal uranium polyhedral. • A unique µ{sub 2}-bridging mode of 4-hydroxybenzoate via alcohol oxygen for 5 f ions. • A 3D framework with uranium polyhedra and µ{sub 4}-terephthalate ligands. • Vibration modes and photoluminescence properties are reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inducing porosity and growing carbon nanofibers in ferroin perchlorate: An example of morphological transitions in coordination complexes

Inducing porosity in solid coordination complex crystals, which are an important class of catalysts, is critical for many applications where a high surface area is required. However, unlike metal organic frameworks (MOFs), fabrication of porous coordination crystals remains a significant challenge. Here we demonstrate a simple method to produce and modulate porosity in coordination complex crystals using ferroin perchlorate, a model system that combines a common ionic complex with a very reactive counter-ion. Using thermal chemical vapor deposition (CVD), we show that by annealing ferroin perchlorate crystals at 350 °C under a flow of ethylene, hydrogen, argon, and oxygen, we induced pores in the crystal. We demonstrate that small amounts of oxygen, which may combine with hydrogen to form water, are essential for pore formation. We also demonstrate that pore size and density can be easily controlled by varying the ethylene flow. Upon raising the annealing temperature to 500 °C, we observed a second transition in which carbon nanofibers (CNFs) grew from the porous crystal. This approach represents a simple and effective method for the synthesis of porous materials with good control over pore size and density. It also enables the synthesis of complex networks of nanostructures (in our case CNFs) by simply varying process parameters such as temperature and gas flows. This represents an important advance for the fabrication of porous coordination complex crystals. - Graphical abstract: Annealing ferroin perchlorate at 350 °C induces porosity in the complex while annealing at 500 °C leads to the additional growth of carbon nanofibers Display Omitted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal structures, and dye removal properties of a series of discrete and polymeric copper, zinc, cobalt, and cadmium complexes containing bis-pyridyl-bis-amine ligands

Two bis-pyridyl-bis-amine ligands, trans-1,2-bis(m-picolyamino)cyclohexane (rac-m-picchxn) and trans-1,2-bis(p-picolyamino)cyclohexane (rac-p-picchxn), derived from trans-1,2-diaminocyclohexane (rac-chxn), were assembled with CuCl{sub 2}, ZnCl{sub 2}, ZnBr{sub 2}, Co(NO{sub 3}){sub 2}, and CdCl{sub 2} through reactants slow diffusion to afford corresponding metal complexes. Complexes [Cu(R,R-m-picchxn)Cl{sub 2}] (1) and [Zn(rac-m-picchxn)Br{sub 2}] (3) are mononuclear coordination structures, complex [Zn{sub 2}(rac-m-picchxn)Cl{sub 4}]{sub n} (2) adopts a one-dimensional (1D) helical chain, complex {[Co(R,R-p-picchxn)(NO_3)_2]·THF·2/3H_2O}{sub n} (4) has a two-dimensional (2D) kgm layer structure, complex [Cd(rac-p-picchxn)Cl{sub 2}]{sub n} (5) suits a 1D double-stranded zigzag chain structure, and compound [Cu(rac-chxn){sub 2}][CuCl{sub 3}] (6) is a Cu(I)-Cu(II) mixed-valence ionic product generated from the hydrolysis of rac-p-picchxn associated with the reduction of Cu(II) ion. The two bis-pyridyl-bis-amine ligands possess a chelating-bridging mode in forming infinite network and a chelating-only mode in forming discrete complexes. These metal–organic architectures show the influence of metal ion combining with organic ligand and anion on the structure variation. Noteworthy, chain polymers 2 and 5 could be utilized in the removal of methyl orange (MO), acid orange 7 (AO7), and malachite green (MG) from water through adsorptive processes. The adsorption dynamics of MO and AO7 on 2 and MG on both 2 and 5 obeyed a pseudo-second-order kinetics while that of MO and AO7 on 5 followed a pseudo-first-order kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗