Metal Complexes In Aqueous Solution Research Articles

Spin propensity in resonant photoemission of transition metal complexes

Resonant photoelectron spectroscopy (RPES) has been used to probe electronic structure properties of the closed-shell ${[{\mathrm{Fe}}^{\mathrm{II}}{(\mathrm{CN})}_{6}]}^{4\ensuremath{-}}$ and open-shell ${[{\mathrm{Fe}}^{\mathrm{III}}{(\mathrm{CN})}_{6}]}^{3\ensuremath{-}}$ prototype transition metal complexes in aqueous solution. Site-selective Fe $2p$ ($L$-edge) RPES maps provide new insight into spin-coupling processes at the core-excited metal centers, with autoionization of ${[{\mathrm{Fe}}^{\mathrm{III}}{(\mathrm{CN})}_{6}]}^{3\ensuremath{-}}$ showing a dramatic ($\ensuremath{\sim}4\ifmmode\times\else\texttimes\fi{}$) singlet versus triplet final-state enhancement. This shows that RPES provides unique opportunities to study spin-dependent electronic properties in transition metal based functional materials.

Catalyst: Challenges in development of adsorbents for recovery of uranium from seawater

Sheng Dai is currently a section head of separations and polymer chemistry and a UT-Battelle Corporate Fellow at the Chemical Sciences Division of the Oak Ridge National Laboratory and a professor of chemistry at the University of Tennessee, Knoxville. He served as a national technical director for a US Department of Energy project aimed at recovering uranium from seawater (2010–2016). His current research interests include ionic liquids, porous materials, and their applications for separation sciences and energy storage, as well as catalysis by nanomaterials.

Neutron Scattering Techniques for Studying Metal Complexes in Aqueous Solution.

Neutron scattering combined with ab initio calculations provides a powerful tool for studying metal complexes in different solvents and, particularly, in water. The majority of traditional characterization techniques in catalysis provide only limited information on homogeneous catalytic processes. Neutron scattering, on the other hand, thanks to its sensitivity to hydrogen atoms, and therefore water molecules, can be used to build detailed models of reaction paths and to observe, at a molecular level, the influence of solvent molecules on a catalytic process. In this Mini-Review we describe several examples on how neutron scattering combined with ab initio calculations can be used to examine the nature of the interaction of water molecules with catalytically active metal complexes in solution.

Photoresponsive host-guest chemistry and relaxation time of fluorinated cyclodextrin and arylazopyrazole-functionalized DOTA metal complexes.

Light-responsive modulation of the longitudinal (T1) and transversal relaxation times of a fluorinated cyclodextrin has been achieved by host-guest complexation with arylazopyrazole-modified metal complexes in aqueous solution. This supramolecular concept can potentially be applied to the development of contrast agents for 19F magnetic resonance imaging (MRI).

A Review on the Electroless Deposition of Functional Materials in Ionic Liquids for Batteries and Catalysis.

Developing functional materials via electroless deposition, without the need of external energy is a fascinating concept. Electroless deposition can be subcategorized into galvanic displacement reaction, disproportionation reaction, and deposition in presence of reducing agents. Galvanic displacement reaction is a spontaneous reduction process wherein the redox potentials of the metal/metal ion in the electrolyte govern the thermodynamic feasibility of the process. In aqueous solutions, the galvanic displacement reaction takes place according to the redox potentials of the standard electrochemical series. In comparison, in the case of ionic liquids, galvanic displacement reaction can be triggered by forming metal ion complexes with the anions of the ionic liquids. Therefore, the redox potentials in ILs can be different to those of metal complexes in aqueous solutions. In this review, we highlight the progress in the electroless deposition of metals and semiconductors nanostructures, from ionic liquids and their application toward lithium/sodium batteries, and in catalysis.

Structural characterization of metal complexes in aqueous solutions: a XAS study of stannous fluoride.

The identity and structure of tin(ii)-fluoride complexes formed in aqueous solutions is determined by combining X-ray absorption spectroscopy, thermodynamic modeling and quantum mechanical calculations. Spectroscopic measurements confirm the presence of 3 stannous fluoride complexes, SnF+, SnF02 and SnF3-, with mean Sn-F bond distances that increase linearly, from 1.98 to about 2.04 Å, as a function of the coordination number. Computational ab initio calculations indicate that the stannous fluoride complexes form localized σs-p bonds, with the stereochemically active lone pair of the Sn(ii) atom distorting the geometry of the complexes. In addition, the SnF3- complex exhibits loosely coordinated water, which is removed upon addition of glycerol to lower the solvent activity. Our results provide spectroscopic confirmation of the stannous fluoride complexes proposed in the literature, and explain why glycerol additions stabilize solutions of Sn(ii) against oxidation.

Electrochemical and Spectrastudies of Some Sulfa Drug Azodyes and Their Metal Complexes in Aqueous Solution

The electrochemical behavior of some azo compounds derived from sulfa drugs derivatives in B.R. buffer solutions of different pH containing 20 (v/v) ethanol was investigated at the mercury electrode using different techniques (DC,DPP,CV and Coulometry) to investigate the effect of medium on the electro reduction process and suggestion the electrode reaction mechanism. The obtained results denoted that these compounds were reduced undergo a single irreversible 4- electron polarographic wave in acid and neutral solutions which represent the cleavage of the N=N center to the amine stage, whereas in alkaline solution, two wave are obtained the second is 2-electron irreversible wave corresponding to the reduction ofCHO group to CH2OH. The DPP and CV data showed a single peak in solutions of pH< 8, whereas three peaks are in alkaline solutions. The dissociation constants of the investigated compounds were determined by using spectrophotometric and potentiometric methods. Also the metal – ligand formation constants were determined potentiometrically and found in the order Cu˃ Co˃ Ni ˃Zn.

Applications of nuclear magnetic resonance to study the structure of platinum-group metal complexes in aqueous solutions

The review includes comprehensive NMR data on platinum metals (99,101Ru, 103Rh, 105Pd, 187Os, 195Pt) and ligand donor atoms (1H, 13C, 14,15N, 17O, 19F, 31P) of metal complexes in aqueous solutions. A systematic analysis of NMR spectroscopy techniques is presented with focus on the measurements of NMR parameters in these systems. A novel concept referred to as coordinate shift is introduced, allowing interpretation of NMR spectra of platinum metal complexes. The review contains an encyclopedic NMR database covering a period of over 50 years from the first measured NMR spectra of platinum metals to 2014.

3D-RISM-MP2 Approach to Hydration Structure of Pt(II) and Pd(II) Complexes: Unusual H-Ahead Mode vs Usual O-Ahead One.

Solvation of transition metal complexes with water has been one of the fundamental topics in physical and coordination chemistry. In particular, Pt(II) complexes have recently attracted considerable interest for their relation to anticancer activity in cisplatin and its analogues, yet the interaction of the water molecule and the metal center has been obscured. The challenge from a theoretical perspective remains that both the microscopic solvation effect and the dynamical electron correlation (DEC) effect have to be treated simultaneously in a reasonable manner. In this work we derive the analytical gradient for the three-dimensional reference interaction site model Møller-Plesset second order (3D-RISM-MP2) free energy. On the basis of the three-regions 3D-RISM self-consistent field (SCF) method recently proposed by us, we apply a new layer of the Z-vector method to the CP-RISM equation as well as point-charge approximation to the derivatives with respect to the density matrix elements in the RISM-CPHF equation to remarkably reduce the computational cost. This method is applied to study the interaction of H2O with the d(8) square planar transition metal complexes in aqueous solution, trans-[Pt(II)Cl2(NH3)(glycine)] (1a), [Pt(II)(NH3)4](2+) (1b), [Pt(II)(CN)4](2-) (1c), and their Pd(II) analogues 2a, 2b, and 2c, respectively, to elucidate whether the usual H2O interaction through O atom (O-ahead mode) or unusual one through H atom (H-ahead mode) is stable in these complexes. We find that the interaction energy of the coordinating water and the transition metal complex changes little when switching from gas to aqueous phase, but the solvation free energy differs remarkably between the two interaction modes, thereby affecting the relative stability of the H-ahead and O-ahead modes. Particularly, in contrast to the expectation that the O-ahead mode is preferred due to the presence of positive charges in 1b, the H-ahead mode is also found to be more stable. The O-ahead mode is found to be more stable than the H-ahead one only in 2b. The energy decomposition analysis (EDA) at the 3D-RISM-MP2 level revealed that the O-ahead mode is stabilized by the electrostatic (ES) interaction, whereas the H-ahead one is mainly stabilized by the DEC effect. The ES interaction is also responsible for the difference between the Pd(II) and Pt(II) complexes; because the electrostatic potential is more negative along the z-axis in the Pt(II) complex than in the Pd(II) one, the O-ahead mode prefers the Pd(II) complexes, whereas the H-ahead becomes predominant in the Pt(II) complexes.

Synthesis and antimicrobial activity of polysaccharide alginate derived cationic surfactant–metal(II) complexes

New natural polysaccharide carbohydrate derivatives of sodium alginate surfactant and its cobalt, copper and zinc complexes were synthesized. Structures of the synthesized compounds are reported using FTIR, 1H NMR and UV–vis. The critical micelle concentration (CMC) value of the alginate surfactant and its metal complexes in aqueous solution was found out from surface tension measurements. Surface tension data at different temperatures served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔGmic, ΔHmic, ΔSmic) and adsorption (ΔGads, ΔGads, ΔSads). The surface activities of the synthesized polymeric surfactant and its metal complexes were influenced by their chemical structures and the type of the transition metals. These compounds were evaluated against Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and fungi (Candida albicans and Asperigllus niger). The antibacterial and antifungal screening tests of the alginate surfactant metal complexes have shown good results compared to its precursor alginate surfactant.

Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes.

Electrochemical electron transfer reactions play an important role in energy conversion processes with many technological applications. Electrodes modified by self-assembled monolayers (SAMs) exhibit reduced double layer effects and are used in molecular electronics. An important quantity for calculating the electron transfer rate constant is the reorganization energy, which is associated with changes in the solute geometry and the environment. In this Letter, an approach for calculating the electrochemical reorganization energy for a redox molecule attached to or near a SAM modified electrode is presented. This integral equations formalism polarizable continuum model (IEF-PCM) approach accounts for the detailed electronic structure of the molecule, as well as the contributions from the electrode, SAM, and electronic and inertial solvent responses. The calculated total reorganization energies are in good agreement with experimental data for a series of metal complexes in aqueous solution. This approach will be useful for calculating electron transfer rate constants for molecular electrocatalysts.

Metal Ion Binding by a G-2 Poly(ethylene imine) Dendrimer. Ion-Directed Self-Assembling of Hierarchical Mono- and Two-Dimensional Nanostructured Materials

The second-generation poly(ethylene imine) dendrimer (L), based on ammonia as the initiating core molecule, forms stable metal complexes in aqueous solution. Speciation of the complex species formed and determination of the relevant stability constants were performed by means of potentiometric titration in 0.10 M NMe(4)Cl solution at 298.1 K. The interaction of L with Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Pb(2+) gives rise to stable complexes with 1:1 (all metal ions), 2:1 (Ni(2+), Cu(2+), Zn(2+), Cd(2+)), 3:2 (Ni(2+), Zn(2+), Cd(2+)), and 3:1 (Cu(2+)) metal/ligand stoichiometries. The crystal structures of [Ni(3)L(2)](ClO(4))(6)·6H(2)O (1) and [Cu(3)LCl(OH)(0.5)(NO(3))(0.5)ox]Cl(1.5)(NO(3))(0.5)·5.5H(2)O (2) were solved by X-ray diffraction. The Ni(3)L(2)(6+) complex cation in 1, existing in solution as a very stable species, shows two dendrimer units linked together by a bridging Ni(2+) ion. In 2, the Cu(3)L(6+) complex cation, which also exists in solution as a very stable species, gives rise, via bridging coordination of oxalate anions, to nanostructured polymeric chains that self-organize into two-dimensional sheets. In both structures, the hierarchical mono- and two-dimensional aggregation is triggered by the action of ionic species behaving either as functional groups on the dendrimer surface (metal ions) or as the glue (metal ions, oxalate) that sticks together dendrimer units. Two association routes, developing via coordinative forces, guide the directional aggregation of dendrimer units: (a) aggregation via metal ions shared by the surfaces of contiguous dendrimer molecules and (b) aggregation via chelating ligands bridging surface metal ions pertaining to contiguous dendrimer molecules. Such aggregation modes provide coordinative routes for the self-assembly of novel families of nanostructured functional materials.

Self-assembly of discrete metal complexes in aqueous solution via block copolypeptide amphiphiles.

The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN)2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN)2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM) showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals). This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

Novel Synthesis Method of Copper Nanoparticles by Controlling Metal Complexes in Aqueous Solution

not Available.

New hydroxypyridinone-functionalized sepharoses as sorbing agents for hard metal ions

Two new polymeric matrices functionalized with 3-hydroxy-4-pyridinone chelating units (HP-NH-SEPH and HP-CNH-SEPH) have been prepared and studied for their chelating ability towards a set of metal ions (e.g. Fe(III), Al(III), and Th(IV)). Both matrices demonstrated excellent ability to complex these metal ions, but HP-NH-SEPH evidenced higher chelating capacity than HP-CNH-SEPH. The corresponding metal-complex gels presented high stability in the pH range 3–7, and their chelating capacity followed the order, Fe(III)≈Th(IV)>Al(III), in agreement with previously reported thermodynamics of the corresponding monomeric ligand–metal complexes in aqueous solution. These functionalized supports also showed capacity to be regenerated and reused. Thus, there are good perspectives for potential environmental and medical applications of these new metal sorbents.

A new reduction route for the synthesis of nanoscale metals and metal oxides with ascorbic acid at low temperature

Reduction of the transition metal complexes in aqueous solution has been investigated systematically by ascorbic acid as the reducing agent without the assistance of any surfactant. Nanoparticles of α-Mn2O3, Ag and Cu were synthesized directly through aqueous phase reduction at room temperature. Nanoscale metal oxides such as Co3O4, α-Fe2O3 and MoO2 were obtained through ascorbic acid reduction in alkali medium at 40°C. All the products were characterized on their structure and micro-morphology by the X-ray diffraction (XRD) and atomic force microscopy (AFM). The particle size of metal and metal oxides was about 10–50 nm. The reaction details and features were described and discussed.

Synthesis, characterization, critical micelle concentration determination, and antimicrobial studies of some complexes of chromium(III) metallosurfactants

Surface active mixed-ligand complexes of Cr(III) containing chelating ligands, namely ethylenediamine (en), triethylenetetramine (trien), 2,2-bipyridine (bpy), and 1,10-phenanthroline (phen) with different axial amine ligands (dodecylamine or cetylamine) were synthesized and characterized by UV–Vis, infrared, and NMR spectroscopies and elemental analysis. The magnetic moments (3.6–3.8 B.M.) are close to the spin-only value for a d3 Cr(III) in octahedral symmetry. The critical micelle concentration values of these surfactant metal complexes in aqueous solution were determined as a function of temperature using conductometric technique. Thermodynamics of micellization (, and ) were evaluated. Dodecyl/cetylamine metallosurfactants obtained were tested for antibacterial and antifungal activities having good activities.

Formalisms for electron-exchange kinetics in aqueous solution and the role of Ab initio techniques in their implementation

Formalisms suitable for calculating the rate of electron exchange between transition metal complexes in aqueous solution are reviewed and implemented in conjunction with ab initio quantum chemical calculations which provide crucial off-diagonal Hamiltonian matrix elements as well as other relevant electronic structural data. Rate constants and activation parameters are calculated for the hex-aquo Fe2 +-Fe3+ system, using a simple activated complex theory, a non-adiabatic semi-classical model which includes nuclear tunnelling, and a more detailed quantum mechanical method based on the Golden Rule. Comparisons are made between calculated results and those obtained by extrapolating experimental data to zero ionic strength. All methods yield similar values for the overall rate constant (a 0.1 L/(mol-sec)). The experimental activation parameters (δHd and δSd) are in somewhat better agreement with the semi classical and quantum mechanical results than with those from the simple activated complex theory, thereby providing some indication that non-adiabaticity and nuclear tunnelling may be important in the Fe2+/3+ exchange reaction. It is concluded that a model based on direct metal-metal overlap can account for the observed reaction kinetics provided the reactants are allowed to approach well within the traditional contact distance of 6.9 a. 6 figures, 7 tables.

Calculating solution redox free energies with ab initio quantum mechanical/molecular mechanical minimum free energy path method

A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids "on-the-fly" QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.

Thermodynamic study of proton transfer reactions of Re(V) trans-dioxocomplexes in aqueous solution

The thermodynamics of protonation of trans-[Re(V)O(2)L(2)](+) (L = aliphatic di and polyamines) complexes in aqueous solution was studied by using experimental and theoretical approaches. The complexes containing diamines undergo protonation on the oxo ligands, whereas those containing polydentate amines protonate on uncoordinated amino groups. The protonation reactions were studied experimentally by microcalorimetric techniques, in all cases exothermic with |DeltaH degrees | ranging from 7 to 50 kJ/mol. For complexes containing diamines, the exothermicity was in concordance with the basicities in some cases, while in others no systematic behaviour was found. For complexes with polydentate amines, the enthalpy dominates with a modest influence on the entropy. Theoretically, Density Functional Theory (DFT) methods were employed in the gas phase, and bulk solvent effects were treated by means of the Polarizable Continuum Model. Direct solute-solvent effects were considered adding explicit water molecules. The enthalpy change calculated in the gas phase was in marked disagreement with the experimental results due to the relevancy of solvation/desolvation processes. The explicit inclusion of water molecules led to a good improvement. A discrete-continuum model was also employed, for which DeltaG degrees was overestimated in all cases. Further investigations, both experimental and theoretical are necessary to get a more complete picture of the proton transfer reactions of these complexes. The experimental values herein determined constitute the first step to construct a set of data to which it is possible to benchmark new theoretical approaches to compute the thermodynamics of proton transfer reactions of metal complexes in aqueous solution.