A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
采用密度泛函理论的M06-2X和MN15方法,研究了生理环境(水液相、1.013×10^(5)Pa、310.15 K)下双丙氨酸螯合二价钙[α-Ala_(2)→Ca^(2+),缩写:α-A_(2)→Ca^(2+)]消除羟基自由基(OH)的反应机理.研究发现,α-A_(2)→Ca^(2+)与OH的反...采用密度泛函理论的M06-2X和MN15方法,研究了生理环境(水液相、1.013×10^(5)Pa、310.15 K)下双丙氨酸螯合二价钙[α-Ala_(2)→Ca^(2+),缩写:α-A_(2)→Ca^(2+)]消除羟基自由基(OH)的反应机理.研究发现,α-A_(2)→Ca^(2+)与OH的反应有抽氢、加成和电子转移3个通道.势能面研究表明:OH与α-A2→Ca^(2+)的抽H反应自由能垒在13.2至56.8 k J/mol之间;OH与α-A_(2)→Ca^(2+)的加成反应自由能垒在61.0至66.2 kJ/mol之间;电子从α-A_(2)→Ca^(2+)向OH转移反应的自由能垒是179.0 k J/mol.结果表明,在生命体内α-A_(2)→Ca^(2+)可通过向OH提供H原子以及OH与C的加成过程消除OH,双丙氨酸螯合钙具有较好的清除羟自由基能力.展开更多
采用密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了苹果酸(MA)在水液相、310.15 K、1.013×10^(5) Pa的生理环境与羟基自由基(OH)及羟基自由基水簇(OH·H_(2)O)的反应机制.MA与OH(H_(2)O)的反应有3...采用密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了苹果酸(MA)在水液相、310.15 K、1.013×10^(5) Pa的生理环境与羟基自由基(OH)及羟基自由基水簇(OH·H_(2)O)的反应机制.MA与OH(H_(2)O)的反应有3个通道,分别是OH(H_(2)O)提H、OH(H_(2)O)与C加成及单电子从MA向OH(H_(2)O)转移.反应能垒及反应焓计算表明:OH(H_(2)O)提H反应是能垒在15.3至52.4 kJ/mol之间的动力学和热力学允许过程;OH(OH·H_(2)O)与C加成反应是能垒在52.4-60.0 k J/mol之间的动力学和热力学允许过程;单电子从MA向OH和OH·H_(2)O转移是能垒分别为299.8和229.1 k J/mol的动力学和热力学不允许过程.结果表明,MA可通过提H和加成反应消除OH,苹果酸可以用做羟自由基清除剂.展开更多
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
文摘采用密度泛函理论的M06-2X和MN15方法,研究了生理环境(水液相、1.013×10^(5)Pa、310.15 K)下双丙氨酸螯合二价钙[α-Ala_(2)→Ca^(2+),缩写:α-A_(2)→Ca^(2+)]消除羟基自由基(OH)的反应机理.研究发现,α-A_(2)→Ca^(2+)与OH的反应有抽氢、加成和电子转移3个通道.势能面研究表明:OH与α-A2→Ca^(2+)的抽H反应自由能垒在13.2至56.8 k J/mol之间;OH与α-A_(2)→Ca^(2+)的加成反应自由能垒在61.0至66.2 kJ/mol之间;电子从α-A_(2)→Ca^(2+)向OH转移反应的自由能垒是179.0 k J/mol.结果表明,在生命体内α-A_(2)→Ca^(2+)可通过向OH提供H原子以及OH与C的加成过程消除OH,双丙氨酸螯合钙具有较好的清除羟自由基能力.
文摘采用密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了苹果酸(MA)在水液相、310.15 K、1.013×10^(5) Pa的生理环境与羟基自由基(OH)及羟基自由基水簇(OH·H_(2)O)的反应机制.MA与OH(H_(2)O)的反应有3个通道,分别是OH(H_(2)O)提H、OH(H_(2)O)与C加成及单电子从MA向OH(H_(2)O)转移.反应能垒及反应焓计算表明:OH(H_(2)O)提H反应是能垒在15.3至52.4 kJ/mol之间的动力学和热力学允许过程;OH(OH·H_(2)O)与C加成反应是能垒在52.4-60.0 k J/mol之间的动力学和热力学允许过程;单电子从MA向OH和OH·H_(2)O转移是能垒分别为299.8和229.1 k J/mol的动力学和热力学不允许过程.结果表明,MA可通过提H和加成反应消除OH,苹果酸可以用做羟自由基清除剂.
