Dual visible and near-infrared luminescence in mononuclear macrocyclic erbium(iii) complexes via ligand and metal centred excitation

Abstract

Considering the structural design of some of the scarce molecular-based Er-centred emitters in the literature, we explored the optical properties of three Er^III hexaazamacrocyclic complexes, namely Er-EDA (1), Er-OPDA(2) and Er-DAP(3). The macrocyclic ligands in these complexes differ in the lateral spacers, and are derived from 2,6-pyridine-dicarbaldehyde and ethylenediamine (EDA), ortho-phenylenediamine (OPDA) or 1,3-diaminopropane (DAP). Upon ligand-centred excitation, the bluish-green and green emissions of the Er^III ion were detected only for the complexes containing macrocycles with aliphatic spacers (1 and 3), which evidenced that these ligands can sensitize the Er^III luminescence. On the other hand, the ligand derived from the aromatic diamine (2) does not sensitize the Er^III luminescence. Energy transfer mechanisms, temperature sensing, CIE coordinates and CCT values were analyzed. Besides the excitation in the ligands, the erbium-centred excitation at 980 nm allowed the detection, in all cases, of bluish-green, green and red up-converted emissions, and also the downshifted NIR emission. The possible mechanisms involved in these transitions were described and analyzed according to the available data.