A novel series of copper(II) complexes of formula [Cu(tren)(mpda)](ClO4)2 · 1/2H2O (1), [Cu2(tren)2(mpda)](ClO4)4 · 2H2O (2), and [Cu2(tren)2(ppda)](ClO4)4 · 2H2O (3) containing the tetradentate tris(2-aminoethyl)amine (tren) terminal ligand and the potentially bridging 1,n-phenylenediamine [n = 3 (mpda) and 4 (ppda)] ligand have been prepared and spectroscopically characterized. X-ray diffraction on single crystals of 1 and 3 show the presence of mono- (1) and dinuclear (3) copper(II) units where the mpda (1) and ppda (3) ligands adopt terminal monodentate (1) and bridging bis(monodentate) (3) coordination modes toward [Cu(tren)]2+ cations with an overall non-planar, orthogonal disposition of the phenylene group and the N-Cu-N threefold axis of the trigonal bipyramid of each copper(II) ion [values of the Cu-N-C-C torsion angle (φsymbol) in the range of 50.8(3)-79.2(2) (1) and 80.9(2)-86.5(2)° (3)]. Variable-temperature magnetic susceptibility measurements on the dinuclear complexes 2 and 3 show the occurrence of moderate ferromagnetic (J = +8.3 cm-1, 2) and strong antiferromagnetic (J = -51.4 cm-1, 3) couplings between the two copper(II) ions across the meta- and para-phenylenediamine bridges, leading to S = 1 (2) and S = 0 (3) ground spin states [H = -JS1 · S2 with S1 = S2 = SCu = 1/2]. Density functional theory (DFT) calculations on the triplet (2) and broken-symmetry (BS) singlet (3) ground spin states, support the occurrence of a spin polarization mechanism for the propagation of the exchange interaction through the predominantly π-type orbital pathway of the 1,n-phenylenediamine bridge. Finally, a new magneto-structural correlation between the magnitude of the magnetic coupling (J) and the Cu-N-C-C torsion angle (φsymbol) has been found which reveals the role of σ- versus π-type orbital pathways in the modulation of the magnetic coupling for m- and p-phenylenediamine-bridged dicopper(II) complexes. © 2009 Elsevier B.V. All rights reserved.
Topological control of the spin coupling in dinuclear copper(II) complexes with meta- and para-phenylenediamine bridging ligands
Marino, Nadia;De Munno, Giovanni;
2010-01-01
Abstract
A novel series of copper(II) complexes of formula [Cu(tren)(mpda)](ClO4)2 · 1/2H2O (1), [Cu2(tren)2(mpda)](ClO4)4 · 2H2O (2), and [Cu2(tren)2(ppda)](ClO4)4 · 2H2O (3) containing the tetradentate tris(2-aminoethyl)amine (tren) terminal ligand and the potentially bridging 1,n-phenylenediamine [n = 3 (mpda) and 4 (ppda)] ligand have been prepared and spectroscopically characterized. X-ray diffraction on single crystals of 1 and 3 show the presence of mono- (1) and dinuclear (3) copper(II) units where the mpda (1) and ppda (3) ligands adopt terminal monodentate (1) and bridging bis(monodentate) (3) coordination modes toward [Cu(tren)]2+ cations with an overall non-planar, orthogonal disposition of the phenylene group and the N-Cu-N threefold axis of the trigonal bipyramid of each copper(II) ion [values of the Cu-N-C-C torsion angle (φsymbol) in the range of 50.8(3)-79.2(2) (1) and 80.9(2)-86.5(2)° (3)]. Variable-temperature magnetic susceptibility measurements on the dinuclear complexes 2 and 3 show the occurrence of moderate ferromagnetic (J = +8.3 cm-1, 2) and strong antiferromagnetic (J = -51.4 cm-1, 3) couplings between the two copper(II) ions across the meta- and para-phenylenediamine bridges, leading to S = 1 (2) and S = 0 (3) ground spin states [H = -JS1 · S2 with S1 = S2 = SCu = 1/2]. Density functional theory (DFT) calculations on the triplet (2) and broken-symmetry (BS) singlet (3) ground spin states, support the occurrence of a spin polarization mechanism for the propagation of the exchange interaction through the predominantly π-type orbital pathway of the 1,n-phenylenediamine bridge. Finally, a new magneto-structural correlation between the magnitude of the magnetic coupling (J) and the Cu-N-C-C torsion angle (φsymbol) has been found which reveals the role of σ- versus π-type orbital pathways in the modulation of the magnetic coupling for m- and p-phenylenediamine-bridged dicopper(II) complexes. © 2009 Elsevier B.V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
