Controlling Ligand Excimer Formation with Dipole Changes in Emissive Rare-Earth/Phosphonic Acid Complexes.

The interactions between substituted arylvinyl phosphonic acid (AVPA) ligands within a Eu-AVPA complex are shown to influence the outcomes of excited state evolution after photoexcitation. Compared with unfunctionalized AVPAs, pairs of ligands functionalized with CF3 in the para position preassociate in the ground state of complexes with Eu3+ according to calculated geometry optimizations. The CF3-substituted AVPA complexes show evidence of red-shifted optical absorption and undergo more efficient excimer formation, as revealed by transient absorption spectroscopy. We rationalize this behavior through simulations of excited-state geometry optimizations that reveal evolution toward interligand phenyl-phenyl planarity for specific excited states. Emission from complexed Eu3+ after energy transfer from the ligand is found to be weaker with CF3 substitution, which we hypothesize is due to intracomplex, interligand aggregates with excimer-promoting geometries. These observations point to the need to consider ground-state geometries as well as dynamic excited-state processes to understand the flow of energy in rare earth coordination complexes.