GIANT CLUSTERS WITH UNUSUAL ELECTRONIC AND MAGNETIC-STRUCTURES DUE TOOPEN-SHELL METAL CENTERS EMBEDDED FAR APART FROM EACH OTHER - SPIN FRUSTRATION AND ANTISYMMETRIC EXCHANGE
D. Gatteschi et al., GIANT CLUSTERS WITH UNUSUAL ELECTRONIC AND MAGNETIC-STRUCTURES DUE TOOPEN-SHELL METAL CENTERS EMBEDDED FAR APART FROM EACH OTHER - SPIN FRUSTRATION AND ANTISYMMETRIC EXCHANGE, Inorganic chemistry, 35(7), 1996, pp. 1926-1934
The magnetic properties of the compounds 4)(21)[{VO(H2O)}6{Mo(mu-H2O)(
2)(mu-OH)Mo}(3){Mo-15 (MoNO)(2)O-58(H2O)(2)}(3)]. 65H(2)P, 1a, O)(2)(m
u-O)Mo}(3){Mo-15(MoNO)(2)O-58(H2O)(2)}(3)]. 14H(2)O, 1b, and H4)(12)[{
Fe(H2O)(2)}(6){Mo(mu-H2O)(2)(mu-OH)Mo}(3) {Mo-15(MoNO)(2)O-58(H2O)(2)}
(3)]. 76H(2)O, 2, have been investigated. 1a, 1b, and 2 contain giant
cluster anions composed of three transferable Mo-17 ligands bridged by
cationic centers which can be exchanged for other metal centers (this
means that metal centers can be placed deliberately on the surface of
large clusters serving as models for metal oxides). Six of these para
magnetic centers (V(IV) in 1a/1b and Fe(III) in 2) are arranged to for
m a trigonal prism. The analysis of the magnetic susceptibility data r
eveals an efficient exchange pathway between the centers located withi
n the trigonal face of this prism mediated by the large and electronic
ally unusual Mo-17 ligands. In the case of the vanadium(IV) compounds
a remarkably strong antiferromagnetic coupling within the triangles (V
... V distances > 650 pm) is observed, ca. 190 cm(-1) for 1a and ca.
160 cm(-1) for 1b, with the Hamiltonian defined as (H) over cap = J Si
gma(i<j)S(i) . S-j. The measurement of the anisotropic susceptibility
of compound 1a allowed us to determine for the first time the elusive
antisymmetric exchange parameter G, expected to be generally operative
in spin frustrated systems. The electronic structure of the giant clu
ster anions of 1a, 1b, and 2 as well as, for the purpose of comparison
, those of the compounds (NH4)(12)[{MoO2}(2){H12Mo15(MONO)(2)O-58(H2O)
(2)} (2)]. 33H(2)O, 3, Na-8[{MoO2}(2){H12Mo15(MoO)(2)O-58 (H2O)(2)}(2)
]. 58H(2)O, 4, and H(2)Me(2))(6)[H2H12((MoO3)-O-VI)(4)(Mo12O40)-O-V],
5, have been investigated by photoelectron spectroscopy and extended H
uckel calculations.