Developing non-conjugated luminescent polymers(NCLPs)with fluorescence and long-lived roomtemperature phosphorescence is of great significance for revealing the essence of NCLPs luminescence,which has gradually attrac...Developing non-conjugated luminescent polymers(NCLPs)with fluorescence and long-lived roomtemperature 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 behaviors 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.Experimental 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 understanding the CL mechanism of NCLPs and provide a new polymer design strategy for the rational design of novel NCLPs materials.展开更多
基金the financial support of the National Natural Science Foundation of China(No.52003254)the Shanxi Scholarship Council of China(No.2020–051)+3 种基金the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2021SX-TD012)the Foundational Research Project of Shanxi Province(Nos.20210302123164,201901D211282,201901D211283)the Science Foundation of North University of China(No.XJJ201925)the MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Zhejiang University(No.2021MSF01)。
文摘Developing non-conjugated luminescent polymers(NCLPs)with fluorescence and long-lived roomtemperature 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 behaviors 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.Experimental 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 understanding the CL mechanism of NCLPs and provide a new polymer design strategy for the rational design of novel NCLPs materials.