Novel Erbium(III)-Encapsulated Complexes Based on ${\pi}$-Extended Anthracene Ligands Bearing G3-Aryl-Ether Dendron: Synthesis and Photophysical Studies

A series of inert and photo-stable Er(III)-encapsulated complexes based on ${\pi}$-extended dendritic anthracene ligands bearing G3-aryl-ether dendron ([G3-AnX]-$CO_2H$), which retain different ${\pi}$-bridging systems, such as single (X= S), double (X= D) and triple (X= T) bonds was designed and synthesized to establish the structure-property relationship. The near infrared emission intensities of Er(III)-encapsulated complexes were enhanced dramatically by increasing the ${\pi}$-conjugated extension of anthracene ligands. The time-resolved luminescence spectra show monoexponential decays with a lifetime of $2.0{\sim}2.4ms$ for $Er^{3+}$ ions in thin films, and calculated intrinsic quantum yields of $Er^{3+}$ ions are in the range of $0.025{\sim}0.03%$. As a result, all Er(III)-encapsulated dendrimer complexes exhibit the near IR emission with the following order: $Er^{3+}-[G3-AnD]_3$(terpy) > $Er^{3+}-[G3-AnS]_3$(terpy) ${\approx}$ $Er^{3+}-[G3-AnT]_3$(terpy), because $Er^{3+}-[G3-AnD]_3$(terpy) has a higher relatively spectral overlap J value and energy transfer efficiency. In addition, the lack of detectable phosphorescence and no significant spectral dependence of the ${\pi}$-extended anthracene moieties on the solvent polarity support energy transfer from their singlet state to the central $Er^{3+}$ ion taking place in $Er^{3+}-[G3-AnX]_3$(terpy).