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• W1978686952 endingPage "7670" @default.
• W1978686952 startingPage "7665" @default.
• W1978686952 abstract "The dinuclear copper(II) complex [Cu2(μ1,1-N3)2(im-2py)2(N3)2] [im-2py = 2-(2-pyridyl)-4,4,5,5-tetramethylimidazolinyl-1-oxy] has been prepared and structurally characterized. The crystal structure consists of a dinuclear unit in which the CuII ions are bridged by two azido ions in a end-on asymmetric fashion and the imino nitroxide radicals are chelating by the two imino N atoms. Accordingly, the magnetic susceptibility data were analyzed considering a linear spin-coupling scheme rad(1)−Cu(2)−Cu(3)−rad(4) (with Si = 1/2, i = 1−4), where the Heisenberg spin Hamiltonian assumes the general form −2∑i<jŜiŜj. Considering only first-neighbor spin-coupling constants (J13 = J24 = J14 = 0), magnetic susceptibility measurements show that the copper(II) imino nitroxide rad−Cu−(Cu−rad)⋮(rad−Cu)−Cu−rad exchange coupling is ferromagnetic and large (J12 = J34 = J1 > +190 cm-1), as is expected for copper imino nitroxide species, and the copper−copper (rad)−Cu−Cu−(rad) coupling through the asymmetric double end-on azide bridges appeared antiferromagnetic and rather large [J23 = J2 = −43(2) cm-1]. By contrast, a density functional theory analysis of the system through the computation of broken-symmetry-state energies resulted in J2 ≈ 0 cm-1. This apparent paradox is resolved by introducing a second-neighbor rad−(Cu)−Cu−(rad)⋮(rad)−Cu−(Cu)−rad spin-coupling constant J13 = J24 = J3, which turns out to be antiferromagnetic both experimentally (when J2 is set equal to zero) and computationally." @default.
• W1978686952 created "2016-06-24" @default.
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• W1978686952 date "2006-08-19" @default.
• W1978686952 modified "2023-09-24" @default.
• W1978686952 title "An Unprecedented Asymmetric End-On Azido-Bridged Copper(II) Imino Nitroxide Complex: Structure, Magnetic Properties, and Density Functional Theory Analysis" @default.
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• W1978686952 doi "https://doi.org/10.1021/ic0606429" @default.
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