A dinuclear MnIII-CuII single-molecule magnet.
The reaction of 1/3 equivalent of CuCl2.2H2O with MnCl2.4H2O and 5-bromo-2-salicylideneamino-1-propanol (H(2)5-Br-sap) in methanol gave dark brown crystals of [MnIIICuIICl(5-Br-sap)2(MeOH)] (1). Complex 1 has an alkoxo-bridged dinuclear core of MnIII and CuII ions, which have elongated octahedral and square-planar coordination geometries, respectively. In dc magnetic susceptibility measurements, chi(m)T values increased as the temperature was lowered, followed by a sudden decrease below 20 K. This behavior is indicative of the occurrence of intramolecular ferromagnetic interactions, and fitting gave an S=5/2 spin ground state with an exchange coupling constant J(MnCu) of +78 cm(-1). Magnetization data collected as a function of temperature and applied magnetic field were analyzed by using a spin Hamiltonian with isotropic Zeeman and axial zero-field splitting (ZFS) terms, and a negative D(5/2) value (-1.86 cm(-1)) was obtained. A high-field EPR (HFEPR) spectrum (342.0 GHz) at 4.2 K was composed of four peaks, and two additional peaks at higher magnetic field appeared as the temperature was increased. The temperature dependences in the HFEPR spectra are indicative of a negative D(5/2) value, and fitting of the data gave D(5/2)=-1.81 cm(-1). In the ac magnetic susceptibility measurements, frequency dependent in-phase (chi(m)') and out-of-phase (chi(m)'') signals with peak maxima at 0.7-1.5 K were observed and small peaks below 0.7 K appeared. The ac susceptibility data supports that 1 is a single-molecule magnet (SMM). Arrhenius plots for the chi(m)'' peaks from 0.7-1.5 K gave the re-orientation energy barrier (DeltaE) of 10.5 K with a pre-exponential factor of 8.2x10(-8) s.
Oshio
Hiroki
H
Department of Chemistry, University of Tsukuba, Tennodai 1-1-1, Tsukuba 305-8571, Japan. oshio@chem.tsukuba.ac.jp
Nihei
Masayuki
M
Yoshida
Ayano
A
Nojiri
Hiroyuki
H
Nakano
Motohiro
M
Yamaguchi
Akira
A
Karaki
Yoshitomo
Y
Ishimoto
Hidehiko
H
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008280:Magnetics; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013696:Temperature
D009942:Organometallic Compounds; D008345:Manganese; D003300:Copper