Optical properties and electronic structure of Eu(III) complexes with HMPA and TPPO.

Two adducts of Eu(III) tris-hexofluoroacetylacetonate with HMPA (OP(N(CH3)2)3, hexamethylphosphotriamide) and TPPO (OP(C6H5)3, triphenylphosphine oxide) were studied by optical spectroscopy and quantum chemistry (DFT/TD-DFT). The structure of the higher occupied molecular orbitals (MO) of the two adducts determines differences in the position of the excitation band maximum of hfac ligands. According to the calculation data, all excited states are caused by the transition to 3 vacant π4* MOs of hfac ligands. Optical spectra of absorption, excitation and luminescence are obtained and interpreted. The peculiarity of the HOMO-LUMO structure, the low value of the energy gap, and the broadened absorption region of hfac ligands compensate the low absorbance ability of the groups N(CH3)2 in a region of 220-360 nm for the adduct Eu(hfac)3(HMPA)2, reducing the luminescence intensity by only 5-10% relative to the adduct of the Eu(III) complex with TPPO ligands.

Electronic structure and optical properties of Ln(III) nitrate adducts with 1,10-phenanthroline.

Adducts of tris-nitrates of rare-earth elements Ce(III), Nd(III), Eu(III), and Er(III) with two molecules of 1,10-phenanthroline with formula Ln(NO3)3(Phen)2 are studied by X-ray photoelectron spectroscopy (XPS) and quantum chemistry (DFT/TDDFT). The geometric structure for DFT modeling is build using X-ray diffraction data. To analyze the composition and differences of the electronic structure in the series under study, XPS spectra were obtained for which interpretation was performed using calculated data. It has been shown that the molecule of Phen, when attached to the complexes of nitrates, is polarized, leads to an increase in absorption in the visible region and reduces the energy gap between HOMO and LUMO. Experimental absorption spectra were obtained, described and interpreted using TDDFT simulation. The transitions in adducts from π to π * MO in Phen ligands determine the main absorption band. The reasons for the absence of luminescence in adducts with ions Ce(III), Nd(III), and Er(III) are revealed by the example of the correlation diagram of singlet and triplet levels. A possible origin of coloring of adducts is determined using TDDFT.