LAUSR

Organic-doped polymers and room-temperature phosphorescence (RTP) mechanisms have been widely reported. However, RTP lifetimes >3 s are rare and RTP-enhancing strategies are incompletely understood. Herein, we demonstrate a rational molecular doping strategy to obtain ultralong-lived, yet bright RTP polymers. The n–π* transitions of boron- and nitrogen-containing heterocyclic compounds can promote a triplet-state population, and the grafting of boronic acid onto polyvinyl alcohol can inhibit molecular thermal deactivation. However, excellent RTP properties were achieved by grafting 1–0.1% (N-phenylcarbazol-2-yl)-boronic acid rather than (2-/3-/4-(carbazol-9-yl)phenyl)boronic acids to afford record-breaking ultralong RTP lifetimes up to 3.517–4.444 s. These results showed that regulation of the interacting position between the dopant and matrix molecules to directly confine the triplet chromophore could more effectively stabilize triplet excitons, disclosing a rational molecular-doping strategy for achieving polymers with ultralong RTP. Based on the energy-donor function of blue RTP, an ultralong red fluorescent afterglow was demonstrated by co-doping with an organic dye.