Effective Photosensitization in Excited-State Equilibrium: Brilliant Luminescence of Tb III Coordination Polymers Through Ancillary Ligand Modifications.

Molecular photosensitizers provide efficient light-absorbing abilities for photo-functional materials. Herein, effective photosensitization in excited-state equilibrium is demonstrated using five Tb III coordination polymers. The coordination polymers are composed of Tb III ions (emission center), hexafluoroacetylacetonato (photosensitizer ligands), and phosphine oxide-based bridges (ancillary ligands). The two types of ligand combinations induces a rigid coordination structure via intermolecular interactions, resulting in high thermal stability (with decomposition temperatures above 300 °C). Excited-triplet-state lifetimes of photosensitizer ligands (τ=120-1320 μs) are strongly dependent on the structure of the ancillary ligands. The photosensitizer with a long excited-triplet-state lifetime (τ≥1120 μs) controls the excited state equilibrium between the photosensitizer and Tb III , allowing the construction of Tb III coordination polymer with high Tb III emission quantum yield (≥70 %).