7 research outputs found
Antiferromagnetic spin chain behavior and a transition to 3D magnetic order in Cu(D,L-alanine)2: Roles of H-bonds
We study the spin chain behavior, a transition to 3D magnetic order and the
magnitudes of the exchange interactions for the metal-amino acid complex
Cu(D,L-alanine)2.H2O, a model compound to investigate exchange couplings
supported by chemical paths characteristic of biomolecules. Thermal and
magnetic data were obtained as a function of temperature (T) and magnetic field
(B0). The magnetic contribution to the specific heat, measured between 0.48 and
30 K, displays above 1.8 K a 1D spin-chain behavior that can be fitted with an
intrachain antiferromagnetic (AFM) exchange coupling constant 2J0 = (-2.12
0.08) cm, between neighbor coppers at 4.49 {\AA} along chains
connected by non-covalent and H-bonds. We also observe a narrow specific heat
peak at 0.89 K indicating a phase transition to a 3D magnetically ordered
phase. Magnetization curves at fixed T = 2, 4 and 7 K with B0 between 0 and 9
T, and at T between 2 and 300 K with several fixed values of B0 were globally
fitted by an intrachain AFM exchange coupling constant 2J0 = (-2.27 0.02)
cm and g = 2.091 0.005. Interchain interactions J1 between coppers
in neighbor chains connected through long chemical paths with total length of
9.51 {\AA} are estimated within the range 0.1 < |2J1| < 0.4 cm, covering
the predictions of various approximations. We analyze the magnitudes of 2J0 and
2J1 in terms of the structure of the corresponding chemical paths. The main
contribution in supporting the intrachain interaction is assigned to H-bonds
while the interchain interactions are supported by paths containing H-bonds and
carboxylate bridges, with the role of the H-bonds being predominant. We compare
the obtained intrachain coupling with studies of compounds showing similar
behavior and discuss the validity of the approximations allowing to calculate
the interchain interactions.Comment: 10 pages, 4 figure
Synthesis and structures of four new compounds of the copper(II)-carboxylate-pyridinecarboxamide system
International audienceThe synthesis and structural characterization of four new copper compounds with formula [Cu(crot)2(isn)2(Hcrot)*H2O] (1), [Cu(oda)(isn)2] (2), [Cu(crot)2(nia)2*(H2O)] (3) and [Cu(oda)(nia)] (4) (crot = trans-2-butenoate, oda = oxydiacetate, isn = isonicotinamide, nia = nicotinamide) is reported. The complexes extend into 3D supramolecular structures by means of hydrogen bonds. EPR spectra of powder samples of the compounds are reported
Magnetism and structure in chains of copper dinuclear paddlewheel units.
International audienceAn anhydrous copper carboxylate compound of formula [Cu(trans-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 9
Pyrophosphate-bridged Cu(II) chain magnet: {[Na3Cu(P2O7)(NO3)].3H2O}n.
International audienceA Cu(II)...Cu(II) pyrophosphate-bridged compound of formula {[Na(3)Cu(P(2)O(7))(NO(3))].3H(2)O}(n) (1) has been characterized. X-ray diffraction measurements show that it crystallizes in the monoclinic space group P2(1)/m, with unit cell dimensions a = 7.2492(5) A, b = 8.2446(6) A, c = 9.9050(7) A, beta = 107.123(1) degrees, and Z = 2. The structure consists of chains of Cu(II) cations at inversion symmetry sites bound to four equatorial oxygen atoms provided by two pyrophosphate anions halved by a symmetry plane and two axial oxygen atoms of nitrate anions. The molar magnetic susceptibility chi(0) of a powdered sample was measured in the temperature range 2 K < T < 273 K, and an isothermal magnetization curve, M(B(0),T), was obtained at T = 30 K, with the magnetic field B(0) between 0 and 5 T. Fitting a spin-chain model to the susceptibility data, we evaluate an antiferromagnetic exchange coupling 2J = -24.3(1) cm(-1) (defined as H(ex) = -2JS(i)S(j)) between Cu(II) neighbors. For any orientation of B(0), single-crystal electron paramagnetic resonance (EPR) spectra obtained at 9.8 and 33.9 GHz at 300 K display a single signal having a g matrix with orthorhombic symmetry, arising from the merger produced by the exchange interaction of the resonances corresponding to the two rotated Cu(II) sites. The g matrices of the individual molecules calculated assuming axial symmetry yielded principal values g(parallel) = 2.367(1) and g(perpendicular) = 2.074(1) at both frequencies, indicating a d(x(2)-y(2)) ground-state orbital for the Cu(II) ions. The angular variation of the EPR line width suggests exchange narrowing in a system with one-dimensional spin dynamics, as expected from the structure and susceptibility data. The results, discussed in terms of the crystal and electronic structures and of the spin dynamics of the compound, are compared with those obtained in other materials