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

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.