Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and...Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22275182,22075272,51973211,51833009,21674111 and 52261135541)the Ministry of Science and Technology of the People’s Republic of China(the National Key R&D Program of China,No.2022YFB4200400)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520102)。
文摘Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.
