以区位异构化的氨基萘酰亚胺(NI)为吸光基团,通过炔键将2个NI区位异构体分别连接到2,2′-联吡啶配体上,制备了2个环Ir(III)配合物.利用稳态吸收与发光光谱、瞬态吸收与发光光谱,并结合理论化学计算,对配合物的光物理性质进行了研究.与...以区位异构化的氨基萘酰亚胺(NI)为吸光基团,通过炔键将2个NI区位异构体分别连接到2,2′-联吡啶配体上,制备了2个环Ir(III)配合物.利用稳态吸收与发光光谱、瞬态吸收与发光光谱,并结合理论化学计算,对配合物的光物理性质进行了研究.与已报道的同类Ir(III)配合物相比,新配合物的可见光吸收能力得到了增强(如在504 nm处摩尔吸光系数达到12000 L mol?1 cm?1),三重激发态寿命得到了延长(达到24.1?s,传统Ir配合物的三重态寿命一般短于5.0?s).此外,纳秒时间分辨瞬态吸收谱以及自旋密度的DFT计算表明,配合物的T1激发态具有明显的配体激发态的特征(3IL激发态),而不是传统Ir(III)配合物的金属到配体的电荷转移激发态(3MLCT激发态).由于新Ir(III)配合物具有强可见光吸收、长寿命三重激发态,所以配合物表现出了较强的三重态湮灭上转换能力.研究结果表明,引入合适的有机吸光配体,采用与配位中心共轭连接的分子结构设计模式,可有效增强配合物的可见光吸收能力,延长三重激发态的寿命;同时,具有区位异构有机吸光基团的Ir(III)配合物,表现出很大差异的光物理性质.本文的研究将有助于制备具有可见光吸收能力的Ir(III)配合物,以及研究有机吸光基团三重激发态.展开更多
利用具有反向系间窜越（RISC）特性的荧光材料4-（Dicyanomethylene）-2-tert-butyl-6-（1,1,7,7-tetramethyljulolidin-4-yl-vinyl）-4H-pyran（DCJTB）制备了掺杂型有机发光器件,并在20~300 K温度范围内测量了器件的磁致发光曲线（即m...利用具有反向系间窜越（RISC）特性的荧光材料4-（Dicyanomethylene）-2-tert-butyl-6-（1,1,7,7-tetramethyljulolidin-4-yl-vinyl）-4H-pyran（DCJTB）制备了掺杂型有机发光器件,并在20~300 K温度范围内测量了器件的磁致发光曲线（即magneto-electroluminescence,MEL）.实验发现,这些MEL曲线表现出奇特的线型：先在低场部分（〈10 m T）小幅度地快速下降,再随着磁场的增加大幅度地缓慢下降,最终低场和高场都表现为负的MEL,这与具有系间窜越的激子型器件的MEL明显不同.另外,MEL曲线在低场和高场的下降幅度都受注入电流和工作温度的调控.通过分析三重态激子参与的自旋相关过程,认为这些负的MEL是由RISC与三重态激子湮灭（TTA）过程共同引起的,并且三重态激子的寿命是影响RISC过程的主要因素.展开更多
Photophysical processes occurring within organic semiconductors is important for designing and fabricating organic solar cells.Copper phthalocyanine(CuPc)is a typical electron acceptor.In this work,the triplet exciton...Photophysical processes occurring within organic semiconductors is important for designing and fabricating organic solar cells.Copper phthalocyanine(CuPc)is a typical electron acceptor.In this work,the triplet exciton lifetime is prolonged by altering the molecular stacking pattern of the CuPc film.For CuPc thin films,the excited state decays are mainly determined by the triplet-triplet annihilation process.The ultrafast transient absorption measurements indicate that the primary annihilation mechanism is one-dimensional exciton diffusion collision destruction.The decay kinetics show a clearly time-dependent annihilation rate constant withγ∝t^(-1/2).Annihilation rate constants are determined to beγ0=(2.87±0.02)×10^(-20)cm^(3)·s^(-1/2)and(1.42±0.02)×10^(-20)cm^(3)·s^(-1/2)for upright and lyingdown configurations,respectively.Compared to the CuPc thin film with an upright configuration,the thin film with a lying-down configuration shows longer exciton lifetime and higher absorbance,which are beneficial to organic solar cells.The results in this work have important implications on the design and mechanistic understanding of organic optoelectronic devices.展开更多
文摘以区位异构化的氨基萘酰亚胺(NI)为吸光基团,通过炔键将2个NI区位异构体分别连接到2,2′-联吡啶配体上,制备了2个环Ir(III)配合物.利用稳态吸收与发光光谱、瞬态吸收与发光光谱,并结合理论化学计算,对配合物的光物理性质进行了研究.与已报道的同类Ir(III)配合物相比,新配合物的可见光吸收能力得到了增强(如在504 nm处摩尔吸光系数达到12000 L mol?1 cm?1),三重激发态寿命得到了延长(达到24.1?s,传统Ir配合物的三重态寿命一般短于5.0?s).此外,纳秒时间分辨瞬态吸收谱以及自旋密度的DFT计算表明,配合物的T1激发态具有明显的配体激发态的特征(3IL激发态),而不是传统Ir(III)配合物的金属到配体的电荷转移激发态(3MLCT激发态).由于新Ir(III)配合物具有强可见光吸收、长寿命三重激发态,所以配合物表现出了较强的三重态湮灭上转换能力.研究结果表明,引入合适的有机吸光配体,采用与配位中心共轭连接的分子结构设计模式,可有效增强配合物的可见光吸收能力,延长三重激发态的寿命;同时,具有区位异构有机吸光基团的Ir(III)配合物,表现出很大差异的光物理性质.本文的研究将有助于制备具有可见光吸收能力的Ir(III)配合物,以及研究有机吸光基团三重激发态.
文摘利用具有反向系间窜越（RISC）特性的荧光材料4-（Dicyanomethylene）-2-tert-butyl-6-（1,1,7,7-tetramethyljulolidin-4-yl-vinyl）-4H-pyran（DCJTB）制备了掺杂型有机发光器件,并在20~300 K温度范围内测量了器件的磁致发光曲线（即magneto-electroluminescence,MEL）.实验发现,这些MEL曲线表现出奇特的线型：先在低场部分（〈10 m T）小幅度地快速下降,再随着磁场的增加大幅度地缓慢下降,最终低场和高场都表现为负的MEL,这与具有系间窜越的激子型器件的MEL明显不同.另外,MEL曲线在低场和高场的下降幅度都受注入电流和工作温度的调控.通过分析三重态激子参与的自旋相关过程,认为这些负的MEL是由RISC与三重态激子湮灭（TTA）过程共同引起的,并且三重态激子的寿命是影响RISC过程的主要因素.
基金supported by the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics at Dalian Institute of Chemical Physics,Chinese Academy of Sciences(No.SKLMRD-K202108)。
文摘Photophysical processes occurring within organic semiconductors is important for designing and fabricating organic solar cells.Copper phthalocyanine(CuPc)is a typical electron acceptor.In this work,the triplet exciton lifetime is prolonged by altering the molecular stacking pattern of the CuPc film.For CuPc thin films,the excited state decays are mainly determined by the triplet-triplet annihilation process.The ultrafast transient absorption measurements indicate that the primary annihilation mechanism is one-dimensional exciton diffusion collision destruction.The decay kinetics show a clearly time-dependent annihilation rate constant withγ∝t^(-1/2).Annihilation rate constants are determined to beγ0=(2.87±0.02)×10^(-20)cm^(3)·s^(-1/2)and(1.42±0.02)×10^(-20)cm^(3)·s^(-1/2)for upright and lyingdown configurations,respectively.Compared to the CuPc thin film with an upright configuration,the thin film with a lying-down configuration shows longer exciton lifetime and higher absorbance,which are beneficial to organic solar cells.The results in this work have important implications on the design and mechanistic understanding of organic optoelectronic devices.
