Magnetism and structure in chains of copper dinuclear paddlewheel units

An anhydrous copper carboxylate compound of formula [Cu(irans-2-butenoate) 2]n has been characterized. X-ray analysis reveals a structure built by paddlewheel units bridged by pairs of Cu ⋯ O axial bonds to give infinite chains arranged In a new topological motif. Susceptibility measurements In the...

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Autor principal: Perec, M.
Otros Autores: Bagglo, R., Sartoris, R.P, Santana, R.C, Peña, O., Calvo, Rafael A.
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 2010
Acceso en línea:Registro en Scopus
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100 1 |a Perec, M. 
245 1 0 |a Magnetism and structure in chains of copper dinuclear paddlewheel units 
260 |c 2010 
270 1 0 |m Perec, M.; INQUIMAE-DQIAQF, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina; email: perec@qi.fcen.uba.ar 
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506 |2 openaire  |e Política editorial 
520 3 |a An anhydrous copper carboxylate compound of formula [Cu(irans-2-butenoate) 2]n has been characterized. X-ray analysis reveals a structure built by paddlewheel units bridged by pairs of Cu ⋯ O axial bonds to give infinite chains arranged In a new topological motif. Susceptibility measurements In the 10-300 K temperature range, and isothermal magnetization curves at 2, 5, 10, and 50 K with fields up to 5 T, were obtained. Electron Paramagnetic Resonance (EPR) spectra of powder samples were measured at 33.9 GHz at 300 K, and at 9.60 GHz at temperatures In the range 90 ≤ T ≤ 350 K. Fitting the susceptibility data to a chain model of alternating paddlewheel and [Cu(μ-O)2Cu] dlnuclear units yielded exchange interactions J1 = -330.6(1) cm-1 and J2 = 5.9(2) cm-1. The EPR spectra reflect the usual antlferromagnetic dinuclear behavior, with zero field splitting parameters of the excited spin triplet, D = -0.329(3) cm-1 and E ∼ 0, plus a central peak not expected for Isolated dinuclear units. We interpret this peak as arising from the stochastic spin dynamics of the chain introduced by exchange couplings between spins in neighbor dinuclear units, which averages out the zero field splitting. Interactions of the units with the rest of the chain acting as a spin bath give rise to a quantum transition between localized dinuclear states and states of the spin chain. This effect competes with the condensation of the antiferromagnetic dinuclear units into the singlet ground state, producing a characteristic temperature dependence of the shape of the powder EPR spectra. We interpret these features In terms of basic theories of magnetic resonance in coupled spin systems applied to the chain array of dinuclear units. © 2009 American Chemical Society.  |l eng 
593 |a INQUIMAE-DQIAQF, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina 
593 |a Comisión Nacional de Energia Atómica, Av. Gral. Paz 1499, 1650 San Martín, Buenos Aires, Argentina 
593 |a Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, INTEC (CONICET-UNL), Güemes 3450, 3000 Santa Fe, Argentina 
593 |a Instituto de Fisica, Universidade Federal de Goiás, Campus Samambaia, CP 131, 74001-970 Goiânia (GO), Brazil 
593 |a UMR 6226 CNRS, Sciences Chimiques de Rennes, Université de Rennes 1, 35042 Rennes, France 
690 1 0 |a BUTYRIC ACID DERIVATIVE 
690 1 0 |a COPPER 
690 1 0 |a ARTICLE 
690 1 0 |a CHEMICAL STRUCTURE 
690 1 0 |a CHEMISTRY 
690 1 0 |a ELECTRON SPIN RESONANCE 
690 1 0 |a MAGNETISM 
690 1 0 |a X RAY CRYSTALLOGRAPHY 
690 1 0 |a BUTYRIC ACIDS 
690 1 0 |a COPPER 
690 1 0 |a CRYSTALLOGRAPHY, X-RAY 
690 1 0 |a ELECTRON SPIN RESONANCE SPECTROSCOPY 
690 1 0 |a MAGNETICS 
690 1 0 |a MODELS, MOLECULAR 
690 1 0 |a MOLECULAR STRUCTURE 
700 1 |a Bagglo, R. 
700 1 |a Sartoris, R.P. 
700 1 |a Santana, R.C. 
700 1 |a Peña, O. 
700 1 |a Calvo, Rafael A. 
773 0 |d 2010  |g v. 49  |h pp. 695-703  |k n. 2  |p Inorg. Chem.  |x 00201669  |w (AR-BaUEN)CENRE-60  |t Inorganic Chemistry 
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