Synthesis and structure of a complex having a quartet ground state with three entirely different spin carriers: Nitronyl nitroxide, o-semiquinone, and Cu-II
Da. Shultz et al., Synthesis and structure of a complex having a quartet ground state with three entirely different spin carriers: Nitronyl nitroxide, o-semiquinone, and Cu-II, INORG CHEM, 39(26), 2000, pp. 6091-6093
A "spin diverse" S = 3/2 ground-state complex, NN-SQCuTp(Cum,Me), has been
prepared. The three S = 1/2 spin carriers are nitronyl nitroxide (NN), o-se
miquinone (o-SQ), and cupric ion. The solid-state structure of the Zn-II de
rivative, NN-SQZnTp(Cum,Me) (C56H69BN8O4Zn), was determined: monoclinic, P2
(1)/c, a = 12.5781(12) Angstrom, b = 17.7408(17) Angstrom, c = 24.440(2) An
gstrom, alpha = 90.00 degrees, beta = 98.240(2)degrees, gamma = 90.00 degre
es, Z = 4. The results of X-ray structural characterization of the Zn-II de
rivative suggest substantial interaction between the two spin carriers NN a
nd o-SQ. Indeed, strong intramolecular exchange coupling has been determine
d by variable-temperature magnetic susceptibility studies. Intraligand ferr
omagnetic exchange is considerably greater than kT, such that only the trip
let state is populated at 300 K, and Cu-II-ligand exchange is ferromagnetic
, with J = +75 cm(-1).