Magnetic properties of ferromagnetic quasi-1D copper-peptide compounds: Exchange interactions and very low temperature phase transitions

The magnetic properties of the Cu(II)-peptide compounds (L-tyrosyl-L-leucinato)Cu(II) and (L-tryptophylglycinato)Cu(II), to be identified as Cu(II)Tyr-Leu and Cu(II)Trp-Gly, respectively, have been investigated by specific heat (0.08 < T < 28 K), dc magnetization (2 < T < 80 K, with B-0 = u(o)H <= 9 T), and ac magnetic susceptibility (with B-0 = 0 for 0.03 < T < 3 K and B-0 up to 9 T for 2 < T < 80 K) measurements. Above similar to 1 K, the specific heat and magnetization of both compounds display a ferromagnetic (FM) spin chain behavior sustained by syn-anti carboxylate bridges connecting equatorially Cu(II) ions at about 5 angstrom. To model this behavior, we calculated the eigenvalues of Heisenberg chains with up to 20 spins 1/2 and used the method of Bonner and Fisher. A global fit of the model to the specific beat and magnetization data gives 2J(0)/k(B) = 3.60(5) K and 2.59(5) K for the intrachain exchange interactions in Cu(II)Tyr-Leu and Cu(II)TrpGly, respectively (H-ex(ij) = -2(J)0 (SiSj)-S-.). These values of 2J(0) are discussed in terms of structural properties of the carboxylate bridges in the two compounds. Using the parameters obtained from the global fit, we calculated isothermal susceptibilities in agreement with the ac susceptibilities measured with small applied dc magnetic fields. However, the ac susceptibility measured with applied dc fields larger than I T lie between the values calculated for the isothermal and adiabatic susceptibilities. At 0.16 K for Cu(II)Tyr-Leu and 0.53 K for Cu(II)Trp-Gly, the observed specific heat and magnetic susceptibility display peaks associated to three-dimensional magnetic phase transitions. The interchain exchange couplings 2J(1) producing the 3D magnetic order are ferromagnetic and have magnitudes 2J(1)/k(B) similar to 0.015 and 0.073 K for Cu(II)Tyr-Leu and Cu(II)TrpGly, respectively.