Thermally activated delayed fluorescent (TADF) coordination polymer with the generation of singlet oxygen

4,4′‐{9,9′‐Spirobi[10H‐acridine]‐10,10′‐diyl}dibenzoic acid ( L , C₂₉H₂₆N₂O₄) was designed and synthesized as a new donor–acceptor motif molecule. Due to the large dihedral angle between the planes of the carboxyphenyl group and the spiroacridine moiety, L possess thermally activated delayed fluorescence (TADF). By applying L as a ligand and using Cd as a metal connector, we synthesized the coordination polymer catena‐poly[hemi‐μ‐aqua‐aqua(μ₃‐4,4′‐{9,9′‐spirobi[10H‐acridine]‐10,10′‐diyl}dibenzoato)cadmium(II)], [Cd(C₂₉H₂₄N₂O₄)(H₂O)_1.5]_n, ( I ). X‐ray crystallographic analysis revealed that this coordination polymer exhibits one‐dimensional chains constructed from molecular twist‐ring moieties, with Cd₂O₁₁ clusters as the connection nodes. The stacking pattern of the two‐dimensional network was formed by C—H…π interactions in the solid state. Similar to L , ( I ) presents a sky‐blue TADF emission, together with a photoluminescence quantum yield (PLQY) of 40%. It is worth noting that the photocatalytic activity toward the generation of singlet oxygen of this coordination polymer is confirmed.