Evolution of the Coordination‐Sphere Symmetry in Copper(II), Nickel(II), and Zinc(II) Complexes with <i>N</i>,<i>N′</i>‐Double‐Armed Diaza‐Crown Ethers: Experimental and Theoretical Approaches

Selmeczi, Katalin; Joly, Jean‐Pierre; Allali, Mustapha; Yeguas, Violeta; Henry, Bernard; Ruiz‐López, Manuel F.

doi:10.1002/ejic.201402432

Cited by 9 publications

(2 citation statements)

References 59 publications

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“…In light of the studies performed on the complexes of L 3 and L 4 , it is likely that the [M(L 1 )] complexes (M = Mn, Co, Cu, and Zn) present seven-coordinated structures with pentagonal bipyramidal coordination environments, while the structure of the Ni 2+ analogue is more difficult to anticipate. To address these fundamental questions, in this work we investigate the structure of the [M(L 1 )] (M = Co, Ni, Cu, or Zn) complexes by using a combination of experimental and theoretical techniques.…”

Section: Introductionmentioning

confidence: 99%

Reasons behind the Relative Abundances of Heptacoordinate Complexes along the Late First-Row Transition Metal Series

et al. 2014

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A series of transition metal complexes [ML(1)] (H2L(1) = 1,4,10-trioxa-7,13-diazacyclopentadecane-N,N'-diacetic acid, M = Co, Ni, Cu, or Zn) have been prepared and characterized. The X-ray structures of the [CoL(1)] and [CuL(1)] complexes reveal that the metal ions are seven-coordinated with a distorted pentagonal bipyramidal coordination. The five donor atoms of the macrocycle define the pentagonal plane of the bipyramid, while two oxygen atoms of the carboxylate groups coordinate apically. The [NiL(1)] complex presents a very distorted structure with long Ni-O distances involving two oxygen atoms of the crown moiety [2.544(3) Å]. This distortion is related to the Jahn-Teller effect that is expected to operate in d(8) pentagonal bipyramidal complexes. The spectroscopic characterization of the [ZnL(1)] and [CuL(1)] complexes using NMR and EPR and the theoretical calculation of the (13)C NMR shifts and g- and A-tensors using DFT confirm that these complexes retain the pentagonal bipyramidal coordination in aqueous solution. The stability trend of the [ML(1)] complexes (Co(2+) > Ni(2+) < Cu(2+) > Zn(2+)), which is in contradiction with the Irving-Williams order, has been analyzed using DFT calculations (TPSSh functional). The free energy values calculated in the gas phase for [CoL(1)](g) + [M(H2O)6](2+)(g) → [ML(1)](g) + [Co(H2O)6](2+)(g) (M = Ni, Cu, Zn) reproduce fairly well the stability trend observed experimentally, the agreement being improved significantly upon inclusion of solvent effects. Our results indicate that the pentagonal bipyramidal coordination is particularly unfavorable for Ni(2+), and thus preorganized ligands that favor this geometry such as L(1) are selective for Co(2+) over Ni(2+) cations.

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Section: Introductionmentioning

confidence: 99%

Reasons behind the Relative Abundances of Heptacoordinate Complexes along the Late First-Row Transition Metal Series

et al. 2014

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“…[16][17][18][19] The crown ethers show binding affinity not only for alkali metal cations, but also for transition metal cations such as Co 2+ , Ni 2+ , Cu 2+ . [20][21][22][23] It has long been believed that the process of cation-complexing is controlled by the cavity of the crown ether, the cation size, and the solvation capability of the solvent.…”

Section: Introductionmentioning

confidence: 99%

Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector

Wang

Hong

et al. 2016

Phys. Chem. Chem. Phys.

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Crown ethers, as a kind of heterocycle, have been the subject of great interest over recent decades due to their selective capability to bind to metal cations. The use of a constant crown ether, such as naphtho-15-crown-5 (N15C5), and varied metal cations (Li, Na, K, Be, Mg, Ca, Co, Ni, Cu) makes it possible to determine the contributions of the metal cations to nonlinear optical (NLO) responses and to design an appropriate NLO-based cation detector. N15C5 and its metal cation derivatives have been systematically investigated by density functional theory. It is found that the dependency of the first hyperpolarizability relies on the metal cation, especially for transition metals. The decrease of the first hyperpolarizabilities for alkali metal cation derivatives is due to their relatively low oscillator strengths, whereas the significant increase of the first hyperpolarizabilities for transition metal cation derivatives can be further illustrated by their low transition energies, large amplitudes and separate distributions of first hyperpolarizability density. Thus, the alkali metal and transition metal cations are distinguishable and the transition metal cations are easier to detect by utilizing the variations in NLO responses.

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Ten-Membered Rings or Larger With One or More Nitrogen and Oxygen and/or Sulfur Atoms

Lee

Ikeda

et al. 2022

Comprehensive Heterocyclic Chemistry IV

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Evolution of the Coordination‐Sphere Symmetry in Copper(II), Nickel(II), and Zinc(II) Complexes with N,N′‐Double‐Armed Diaza‐Crown Ethers: Experimental and Theoretical Approaches

Cited by 9 publications

References 59 publications

Reasons behind the Relative Abundances of Heptacoordinate Complexes along the Late First-Row Transition Metal Series

Reasons behind the Relative Abundances of Heptacoordinate Complexes along the Late First-Row Transition Metal Series

Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector

Ten-Membered Rings or Larger With One or More Nitrogen and Oxygen and/or Sulfur Atoms

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