Hydrogen bonding-induced oxygen clusters and long-lived room temperature phosphorescence from amorphous polyols

Developing non-conjugated luminescent polymers (NCLPs) with fluorescence and long-lived room -temperature phosphorescence is of great significance for revealing the essence of NCLPs luminescence, which has gradually attracted the attention of researchers in recent years. Herein, polymethylol (PMO) and poly(3-butene-1,2-diol) (PBD) with polyhydroxy structures were prepared and their luminescence be-haviors were investigated to reveal the clusteroluminescence (CL) mechanism. Compared with polyvinyl alcohol with non-luminescent behavior, PMO and PBD exhibit cyan-blue fluorescence with quantum yields of ca. 12% and green room-temperature phosphorescence with lifetimes of ca. 89 ms in the solid state. Both fluorescence and phosphorescence exhibit typical excitation-dependent CL behavior. Exper-imental and theoretical analyses show that the strong hydrogen-bonding interaction of PMO and PBD greatly promotes the formation of oxygen clusters and the through-space n-n interaction of oxygen atoms, enabling fluorescence and phosphorescence emission. Our results have enormous implications for under-standing the CL mechanism of NCLPs and provide a new polymer design strategy for the rational design of novel NCLPs materials.(c) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

Developing non-conjugated luminescent polymers (NCLPs) with fluorescence and long-lived room-temperature phosphorescence is of great significance. The study investigates the luminescence behavior of polymethylol (PMO) and poly(3-butene-1,2-diol) (PBD) to reveal the clusteroluminescence (CL) mechanism. The results provide insights into the understanding of the CL mechanism of NCLPs and offer a new polymer design strategy for novel NCLP materials.