Ta. Hopkins et al., ELECTRONIC-STATE STRUCTURE AND OPTICAL-PROPERTIES OF TB(ODA)(3)(3-) COMPLEXES IN TRIGONAL 3[TB(ODA)(3)]CENTER-DOT-2NACLO(4)CENTER-DOT-6H(2)O CRYSTALS, Inorganic chemistry, 37(6), 1998, pp. 1401-1412
Polarized optical absorption and emission measurements are used to loc
ate and assign 95 crystal-field energy levels split out of the 4f(8) e
lectronic configuration of Tb3+ in single crystals of Na-3[Tb(oda)(3)]
. 2NaClO(4) . 6H(2)O (where oda denotes an oxydiacetate ligand). The a
bsorption measurements span the 235-490 nm wavelength range, and the e
mission measurements span the 485-685 nm wavelength range. The combine
d absorption and emission spectra measurements provide access to the e
nergy-level structures of 46 different 4f(8)[SL]J multiplet manifolds
of Tb3+ (all multiplet manifolds with baricenter energies <42 400 cm(-
1) above ground). The site symmetry of the Tb3+ ions in Na-3[Tb(oda)(3
)]. 2NaClO(4) . 6H(2)O is D-3, and the point-group symmetry of the tri
sterdentate Tb(oda)(3)(3-) coordination complexes is also D-3. The Tb(
oda)(3)(3-) complexes are chiral, and they exist in just one, fully re
solved enantiomeric form in single crystals of Na-3[Tb(oda)(3)]. 2NaCl
O(4) . 6H(2)O. The crystals exhibit strong chiroptical activity in the
ir absorption and emission spectra, and results obtained from both cir
cularly polarized and linearly polarized optical spectra measurements
are used in making transition line assignments. The energy-level data
acquired from the spectroscopic measurements are analyzed in terms of
a model Hamiltonian that includes consideration of both isotropic and
nonisotropic 4f electron/crystal-field interactions, and the interacti
on parameters derived from this analysis are discussed and then compar
ed with those obtained for other Na-3[Ln(oda)(3)]. 2NaClO(4) . 6H(2)O
systems and for Tb3+ in other crystalline hosts.