Journal of the American Chemical Society, Vol.135, No.8, 3017-3026, 2013
Giant Ising-Type Magnetic Anisotropy in Trigonal Bipyramidal Ni(II) Complexes: Experiment and Theory
This paper reports the experimental and theoretical investigations of two trigonal bipyramidal Ni(II) complexes, [Ni(Me(6)tren)Cl](ClO4) (1) and [Ni(Me(6)tren)Br](Br) (2). High-field, high-frequency electron paramagnetic resonance spectroscopy performed on a single crystal of 1 shows a giant uniaxial magnetic anisotropy with an experimental D-expt value (energy difference between the M-s = +/- 1 and M-s = 0 components of the ground spin state S = 1) estimated to be between -120 and -180 cm(-1). The theoretical study shows that, for an ideally trigonal Ni(II) complex, the orbital degeneracy leads to a first-order spin-orbit coupling that results in a splitting of the M-s = +/- 1 and M-s = 0 components of approximately -600 cm(-1). Despite the Jahn-Teller distortion that removes the ground term degeneracy and reduces the effects of the first-order spin orbit interaction, the D value remains very large. A good agreement between theoretical and experimental results (theoretical D-theor, between -100 and -200 cm(-1)) is obtained.