Single End‐to‐End Azidocopper(II) Chain Based on an Electroactive Ligand: A Structural, Electrochemical, Magnetic and Ab Initio Study

Pilet, Guillaume; Médebielle, Maurice; Tommasino, Jean Bernard; Chastanet, Guillaume; Guennic, Boris Le; Train, Cyrille

doi:10.1002/ejic.200900575

Cited by 10 publications

(5 citation statements)

References 98 publications

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“…Calculations have been performed on two distinct dinuclear models (Figure ), namely, 4a , which illustrates a potential intramolecular Cu1···Cu1b interaction, and 4b , which takes into account a possible Cu1···Cu1c interaction via nitrate/water hydrogen bonds. Such a strategy to consider a succession of dinuclear units (like in compound 4 ) has already been used successfully in previous studies on magnetic chains. , This bottom-up-like approach should shed some light on the origin (i) of the antiferromagnetic behavior observed in 4 and (ii) of the relative participation of the different dinuclear subunits by the evaluation of J a and J b .…”

Section: Resultsmentioning

confidence: 99%

“…Such a strategy to consider a succession of dinuclear units (like in compound 4) has already been used successfully in previous studies on magnetic chains. 95,96 This bottom-up-like approach should shed some light on the origin (i) of the antiferromagnetic behavior observed in 4 and (ii) of the relative participation of the different dinuclear subunits by the evaluation of J a and J b .…”

Section: ' Results and Discussionmentioning

confidence: 99%

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Coexistence of Intramolecular Ligand-Mediated and Through Hydrogen-Bond Magnetic Interactions in a Chain of Dicopper(II) Units

et al. 2011

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The reaction of 2,8-dimethyl-5,11-bis(pyridin-2-ylmethyl)-1,4,5,6,7,10,11,12-octahydroimidazo[4,5-h]imidazo[4,5-c][1,6]-diazecine (dimp) with copper(II) nitrate in water produces the compound [Cu(2)(dimp)(H(2)O)(2)(NO(3))(2)](NO(3))(2). The single-crystal X-ray structure shows the formation of hydrogen-bonded chains in the lattice that are formed by dicopper(II) units doubly connected by nitrate/water bridges. Within the one-dimensional chains, the Cu ions are separated by either intramolecular or intermolecular distances of 7.309(2) Å or 6.255(2) Å, respectively. The magnetic susceptibility data revealing weak antiferromagnetic exchange interactions between the copper(II) ions were interpreted by considering two possible models, namely, an isolated dinuclear and a 1-D chain picture. The latter leads to an alternation J(1) = -11.6 and J(2) = -3.0 cm(-1) along the chain. In order to clarify the relative strengths of the exchange couplings through hydrogen bonds and via the bridging dimp ligand, solution EPR studies and quantum chemical calculations were carried out. EPR studies unambiguously conclude on the existence of an exchange interaction J(a) mediated by the dinucleating dimp ligand, while the through-H coupling J(b) is physically absent in solution. On the basis of dinuclear units extracted from the X-ray data, J(a) was estimated around -5.0 cm(-1) from DFT-based calculations (M06 functional), whereas J(b) is negligible. In contrast, wave function configuration interaction calculations (DDCI) support a description where both inter- and intramolecular pathways coexist with a preeminent role of H bonds with J(a) = -2.8 and J(b) = -10.4 cm(-1). Not only are these values very consistent with the extracted set of parameters (J(1), J(2) = -11.6, -3.0 cm(-1)) but the possibility to generate leading exchange coupling through weak bonds is evidenced by means of wave function-based calculations.

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Section: Resultsmentioning

confidence: 99%

Section: ' Results and Discussionmentioning

confidence: 99%

Coexistence of Intramolecular Ligand-Mediated and Through Hydrogen-Bond Magnetic Interactions in a Chain of Dicopper(II) Units

et al. 2011

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“…Cu-O,N bond lengths within the four complexes are similar: 1.910(3) and 1.941(3) Å for A, 1.897(3) and 2.008(4) Å for B, 1.897(4) and 2.018(4) Å for C and from 1.897(6) to 1.958(6) Å for D, which are in good agreement with literature values. [27,28] A A second way to evaluate the distortion from an ideal square planar environment is to measure the angle, the ω parameter, between the planes formed by the enaminone moiety of two ligands (A, B and C) with the central metal atom or of one ligand (D) with the Cu II ion ( Figure 5). Another parameter, β, which is used to evaluate the distortion of the local geometry of the metal centre, is defined as a www.eurjic.orghalf of the value of the mean trans ligand-metal-ligand angle, which is 90°for square planar geometry (D 4h ) and 54.7°f or tetrahedral geometry (T d ).…”

Section: Crystal Structure Descriptionmentioning

confidence: 99%

Bidentate and Tetradentate β‐Aminovinyl Trifluoromethylated Ketones and Their Copper(II) Complexes: Synthesis, Characterization and Redox Chemistry

2012

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Keywords: Electrochemistry / UV/Vis spectroscopy / Copper / FluorineNew polyfunctional bidentate and tetradentate trifluoromethylated enaminone ligands that bear redox-active and photosensitive moieties were synthesized in moderate to good yields and their coordination chemistry with copper(II) was examined. The crystal structures revealed the formation of mononuclear Cu II complexes with all ligands, where the metal ion is located in almost perfect to distorted square planar environments. The deviation from an ideal square

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“…Despite the huge interest on Cu(II)/Cu(I) electron transfer processes in biological systems, 20 only a few studies were carried out on Cu(II) complexes based on azide linkers. 17,21 It probably mainly follows on from the interest in its magnetic coupler ability.…”

Section: Electrochemical Studiesmentioning

confidence: 99%

A 1D coordination polymer built on asymmetric μ1,1,3-azide bridge: from unusual topology to magnetic properties and Cu(ii)/Cu(i) redox reversibility

Tommasino¹,

Chastanet²,

Guennic³

et al. 2012

New J. Chem.

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An azide-bridged Cu(II) one dimensional polymer was synthesized in a one pot reaction in the presence of ammonia. The refined crystal structure evidenced the unusual asymmetric m 1,1,3 coordination mode of the azide ion leading to a {Cu(m 1,1,3-N 3)(m 1-N 3)(NH 3) 0.8 (H 2 O) 1.2 } n chain. The redox process of this complex was studied by cyclic voltammetry evidencing the Cu(II)/Cu(I) reversibility. Magnetic measurements were interpreted as a uniform antiferromagnetic chain (J = À15.2 cm À1) holding rather strong inter-chain exchange (zJ 0 = À2.8 cm À1). Multireference difference dedicated configuration interaction (DDCI) calculations confirmed the non-negligible intensity of inter-chain interactions and evidenced a strong influence of the type of coordinated solvent, NH 3 or H 2 O, on the nature and magnitude of the magnetic exchange.

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Single End‐to‐End Azidocopper(II) Chain Based on an Electroactive Ligand: A Structural, Electrochemical, Magnetic and Ab Initio Study

Cited by 10 publications

References 98 publications

Coexistence of Intramolecular Ligand-Mediated and Through Hydrogen-Bond Magnetic Interactions in a Chain of Dicopper(II) Units

Coexistence of Intramolecular Ligand-Mediated and Through Hydrogen-Bond Magnetic Interactions in a Chain of Dicopper(II) Units

Bidentate and Tetradentate β‐Aminovinyl Trifluoromethylated Ketones and Their Copper(II) Complexes: Synthesis, Characterization and Redox Chemistry

A 1D coordination polymer built on asymmetric μ1,1,3-azide bridge: from unusual topology to magnetic properties and Cu(ii)/Cu(i) redox reversibility

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