Effective photosensitized emission of a Tb(III) complex using a β-diketonate photosensitizer and an oxygen barrier system in a thermally populated triplet state.

Abstract

Photosensitizer design of luminescent terbium (Tb(III)) complexes with narrow bandwidths is important for advancing luminescent materials. In this study, we report an effective photosensitizer model in a thermally populated lowest excited triplet (T1) state during Tb(III) emission. The Tb(III) complex comprises a Tb(III) ion (serving as an emission center), hexafluoroacetylacetonates (acting as photosensitizer ligands), and bulky cyclohexyl group-attached phosphine-oxide-type ligands (functioning as an oxygen barrier system). Emission properties including emission and excitation spectra, ligand-excited emission quantum yields, and emission lifetimes were evaluated in the absence and presence of oxygen. Coordination geometry structures were determined through analysing single-crystal structures. The electronic structure based on 4f-orbitals was estimated from radiative rate constants and quantum chemical calculations. The bulky phosphine oxide ligand not only provides an oxygen barrier system but also induces an electronic structural modulation based on 4f-orbitals, allowing for effective photosensitized Tb(III) emission in a thermally populated ligand T1 state in air.