Electronic State Structure and Optical Properties of Tb(oda)33- Complexes in Trigonal Na3[Tb(oda)3]·2NaClO4·6H2O Crystals†

Polarized optical absorption and emission measurements are used to locate and assign 95 crystal-field energy levels split out of the 4f 8 electronic configuration of Tb3+ in single crystals of Na3[Tb(oda)3]·2NaClO4·6H2O (where oda denotes an oxydiacetate ligand). The absorption measurements span the 235−490 nm wavelength range, and the emission measurements span the 485−685 nm wavelength range. The combined absorption and emission spectra measurements provide access to the energy-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 Na3[Tb(oda)3]·2NaClO4·6H2O is D3, and the point-group symmetry of the tris-terdentate Tb(oda)33- coordination complexes is also D3. The Tb(oda)33- complexes are chiral, and they exist in just one, fully resolved enantiomeric form in single crystals of Na3[Tb(oda)3]·2NaClO4·6H2O. The crystals exhibit strong chiroptical activity in their absorption...