Sensitized luminescence properties of dinuclear lanthanide macrocyclic complexes bearing a benzophenone antenna

Dinuclear lanthanide (Ln=Tb3+ or Eu3+) complexes (Ln2L2) of two octadentate macrocyclic polyaminopolycarboxylic ligands connected through a benzophenone (BP) moiety (L2) have been synthesized. Sensitized luminescence properties of Ln2L2 in water have been studied in comparison to those of BP-conjugated mononuclear Ln complexes (LnL1). The luminescence intensity of Tb2L2 is lower than that of TbL1 because of lower triplet quantum yield of the BP moiety. In contrast, Eu2L2 shows higher intensity than EuL1. For both Eu complexes, energy level of triplet excited-state BP (3BP*) is only 3 kJ mol−1 higher than that of 5D2 excited-state of Eu3+. The 5D2 state formed by a triplet-energy transfer (TET) from 3BP* is therefore deactivated by a back energy transfer (BET) to the ground-state BP, resulting in low luminescence intensity of EuL1. In contrast, within Eu2L2, TET from 3BP* to 5D0 state of two Eu3+ ions is accelerated, thus leading to higher luminescence intensity. Another notable feature of Eu2L2 is the luminescence quantum yield independent of its concentration. In contrast, for EuL1 system, an intermolecular BET occurs from 5D2 state of Eu3+ to the ground-state BP conjugated to another EuL1 complex, resulting in a yield decrease with the concentration increase.