Quantification of Outer-Sphere Macrochelate Formation in the Ternarycis-Diammine−Platinum(II)−Bis-2‘-deoxyguanosine 5‘-Monophosphate Complex,cis-(NH3)2Pt(dGMP)22-, and Formation of Quaternary Mixed Metal Ion Species with Magnesium(II), Copper(II), or Zinc(II) in Aqueous Solution

1998 ◽  
Vol 37 (19) ◽  
pp. 4857-4864 ◽  
Author(s):  
Bin Song ◽  
Gerda Oswald ◽  
Jing Zhao ◽  
Bernhard Lippert ◽  
Helmut Sigel
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Outer Sphere ◽  
Mixed Metal ◽  
Ion Species

scholarly journals A Single Crystal Hybrid Ligand Framework of Copper(II) with Stable Intrinsic Blue-Light Luminescence in Aqueous Solution

Nanomaterials ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 2281
Author(s):  
Suwitra Charoensuk ◽  
Jing Tan ◽  
Mohini Sain ◽  
Hathaikarn Manuspiya
Keyword(s):  
Aqueous Solution ◽  
Single Crystal ◽  
Metal Ion ◽  
Three Dimensional ◽  
Supramolecular Interactions ◽  
Dual Phase ◽  
Intense Luminescence ◽  
Solid Liquid ◽  
External Stimuli ◽  
Ion Species

Single-crystal solid–liquid dual-phase hybrid organic–inorganic ligand frameworks with reversible sensing response facilitated by external stimuli have received significant attention in recent years. This report presents a significant leap in designing electronic structures that display reversible dual-phase photoluminescence properties from single-crystal hybrid ligand frameworks. Three-dimensional Cu(C3N2H4)4Cl2 complex frameworks were formed through the intermolecular hydrogen bonding and π⋯π stacking supramolecular interactions. The absorption band peaks at 627 nm were assigned to d–d transition showing 10Dq = 15,949 cm−1 and crystal field stabilization energy (CFSE) = 0.6 × 10Dq = 114.4 kJmol−1, while the ligand-to-metal charge transfer (LMCT) of complexes was displayed at 292 nm. The intense luminescence band results from LMCT present at 397 nm. Considering its structure, air stability, framework forming and stable luminescence in aqueous solution, the Cu(C3N2H4)4Cl2 complex shows potential for luminescence Cu-based sensors using emission intensity to detect heavy metal ion species.

Outer-sphere charge transfer in mixed-metal ion pairs

1982 ◽  
Vol 21 (4) ◽  
pp. 1562-1571 ◽  
Author(s):  
Jeff C. Curtis ◽  
Thomas J. Meyer
Keyword(s):  
Charge Transfer ◽  
Metal Ion ◽  
Ion Pairs ◽  
Outer Sphere ◽  
Mixed Metal

Kinetics and mechanism of the reaction of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione

1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics And Mechanism ◽  
Kinetic Constants ◽  
Steric Factors ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reactions of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione to form the corresponding monocomplexes have been studied spectrophotometrically in the range 5 °C to 16 °C at I 25 mol l-1 in aqueous solution. In the proposed mechanism for the two complexes, the enol form reacts with the metal ion by parallel acid-independent and inverse-acid paths. The kinetic constants for both pathways have been calculated at five temperatures. Activation parameters have also been calculated. The results are consistent with an associative activation for Fe(H2O)63+ and dissociative activation for Fe(H2O)5(OH)2+. The differences in the results for the complexes of heptanediones studied are interpreted in terms of steric factors.

Protonation effects on dynamic flux properties of aqueous metal complexes

2009 ◽  
Vol 74 (10) ◽  
pp. 1543-1557 ◽  
Author(s):  
Herman P. Van Leeuwen ◽  
Raewyn M. Town
Keyword(s):  
Complex Formation ◽  
Metal Ion ◽  
Good Description ◽  
Minor Component ◽  
Outer Sphere ◽  
Metal Species ◽  
Central Metal ◽  
Inner Sphere ◽  
A Minor ◽  
Protonated Ligand

The degree of (de)protonation of aqueous metal species has significant consequences for the kinetics of complex formation/dissociation. All protonated forms of both the ligand and the hydrated central metal ion contribute to the rate of complex formation to an extent weighted by the pertaining outer-sphere stabilities. Likewise, the lifetime of the uncomplexed metal is determined by all the various protonated ligand species. Therefore, the interfacial reaction layer thickness, μ, and the ensuing kinetic flux, Jkin, are more involved than in the conventional case. All inner-sphere complexes contribute to the overall rate of dissociation, as weighted by their respective rate constants for dissociation, kd. The presence of inner-sphere deprotonated H2O, or of outer-sphere protonated ligand, generally has a great impact on kd of the inner-sphere complex. Consequently, the overall flux can be dominated by a species that is a minor component of the bulk speciation. The concepts are shown to provide a good description of experimental stripping chronopotentiometric data for several protonated metal–ligand systems.

scholarly journals H2O coordination in macropa complexes of f elements (Ac, La, Lu): feasibility of the 11th coordination site

2021 ◽  
Author(s):  
Attila Kovács ◽  
Zoltán Varga
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Density Functional ◽  
Molecular Level ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Coordination Site ◽  
Additional Ligand ◽  
Ligand Coordination ◽  
Bonding Properties

AbstractThe feasibility of an additional ligand coordination at the 11th coordination site of actinium, lanthanum, and lutetium ions in 10-fold coordinated macropa complexes has been studied by means of density functional theory calculations. The study covered the two main macropa conformers, Δ(δλδ)(δλδ) and Δ(λδλ)(λδλ), favoured by larger (Ac3+, La3+) and smaller (Lu3+) ions, respectively. At the molecular level, the coordination of H2O is the most favourable to the largest Ac3+ while only slightly less to La3+. Protonation of the picoline arms enhances the coordination by shifting the metal ion closer to the open site of the ligand. The choice of macropa conformer has only a slight influence on the strength and bonding properties of the H2O coordination. Aqueous solution environment decreases considerably the energy gain of H2O coordination at the 11th coordination site.

Determination of the complexation properties of a crosslinked poly(acrylic acid) gel with copper(II), nickel(II), and lead(II) in dilute aqueous solution

2001 ◽  
Vol 79 (4) ◽  
pp. 370-376 ◽  
Author(s):  
Catherine Morlay ◽  
Yolande Mouginot ◽  
Monique Cromer ◽  
Olivier Vittori
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Acrylic Acid ◽  
Metal Ion ◽  
Conditional Stability ◽  
Binding Properties ◽  
Complex Species ◽  
Complexing Capacity ◽  
Dilute Aqueous Solution ◽  
Poly Acrylic Acid

The possible removal of copper(II), nickel(II), or lead(II) by an insoluble crosslinked poly(acrylic acid) was investigated in dilute aqueous solution. The binding properties of the polymer were examined at pH = 6.0 or 4.0 with an ionic strength of the medium µ = 0.1 or 1.0 M (NaNO3) using differential pulse polarography as an investigation means. The highest complexing capacity of the polyacid was obtained with lead(II) at pH = 6.0 with µ = 0.1 M, 4.8 mmol Pb(II)/g polymer. The conditional stability constants of the complex species formed were determined using the method proposed by Ruzic assuming that only the 1:1 complex species was formed; for lead(II) at pH = 6.0 and µ = 0.1 M, log K' = 5.3 ± 0.2. It appeared that the binding properties of the polymer increased, depending on the metal ion, in the following order: Ni(II) < Cu(II) < Pb(II). The complexing capacity and log K' values decreased with the pH or with an increase of the ionic strength. These results were in agreement with the conclusions of our previous studies of the hydrosoluble linear analogues. Finally, with the insoluble polymer, the log K' values were comparable to those previously obtained with the linear analogue whereas the complexing capacity values expressed in mmol g-1 were slightly lower.Key words: insoluble crosslinked poly(acrylic acid), copper(II), nickel(II), and lead(II) complexation.

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