The First Inert and Photostable Encapsulated Lanthanide(III) Complexes Based on Dendritic 9,10‐Diphenylanthracene Ligands: Synthesis,Strong Near‐Infrared Emission Enhancement,and Photophysical Studies

A series of inert and photostable encapsulated lanthanide(III) complexes—based on dendritic anthracene ligands—is shown for the first time to exhibit strong near‐IR emission bands via efficient energy transfer from the excited states of the peripheral antenna to the Ln³⁺ ions (Er³⁺, Yb³⁺, and Nd³⁺). A significant decrease in the fluorescence of the anthracene ligand is accompanied by a strong increase in the near‐IR emission of the Ln³⁺ ions. The near‐IR emission intensities of Ln³⁺ ions in the encapsulated Ln³⁺–dendrimer complexes are dramatically enhanced on increasing the generation number (n) of dendrons, owing to site‐isolation and light‐harvesting effects. Furthermore, a first attempt is made to distinguish between the site‐isolation and light‐harvesting effects in the present complexes. Photophysical studies indicate the sensitization of Ln³⁺ luminescence by energy transfer through the excited singlet state of the anthracene ligands, and the energy‐transfer efficiency between the dendritic anthracene ligands and the Ln³⁺ ion is evaluated to be in the range of 90 to 97 %. Their energy‐transfer efficiency is in good agreement with the result that the biexponential decays contain a radiative decay of anthracene units (< ca. 10 %) and an energy‐transfer component (> ca. 90 %) from the excited state of anthracene ligands to the Ln³⁺ ions. Time‐resolved luminescence spectra show monoexponential decays with a lifetime of 2 μs for the Er³⁺ ion 11 μs for the Yb³⁺ ion and 0.7 μs for the Nd³⁺ ion in thin films, and calculated intrinsic quantum yields of the Ln³⁺ ions are in the range of ca. 0.025 to 0.55 %.