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Substituent effects on the photophysical properties of 2,9‐substituted phenanthroline copper(I) complexes: a theoretical investigation
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-11-26 , DOI: 10.1002/cphc.202000868 Chantal Daniel 1 , Christophe Gourlaouen 2 , Keiko Takano 3 , Ai Hamano 4
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-11-26 , DOI: 10.1002/cphc.202000868 Chantal Daniel 1 , Christophe Gourlaouen 2 , Keiko Takano 3 , Ai Hamano 4
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The electronic and nuclear structures of a series of [Cu(2,9‐(X)2‐phen)2]+ copper(I) complexes (phen=1,10‐phenanthroline; X=H, F, Cl, Br, I, Me, CN) in their ground and excited states are investigated by means of density functional theory (DFT) and time‐dependent (TD‐DFT) methods. Subsequent Born‐Oppenheimer molecular dynamics is used for exploring the T1 potential energy surface (PES). The T1 and S1 energy profiles, which connect the degenerate minima induced by ligand flattening and Cu−N bond symmetry breaking when exciting the molecule are calculated as well as transition state (TS) structures and related energy barriers. Three nuclear motions drive the photophysics, namely the coordination sphere asymmetric breathing, the well‐documented pseudo Jahn‐Teller (PJT) distortion and the bending of the phen ligands. This theoretical study reveals the limit of the static picture based on potential energy surfaces minima and transition states for interpreting the luminescent and TADF properties of this class of molecules. Whereas minor asymmetric Cu−N bonds breathing accompanies the metal‐to‐ligand‐charge‐transfer re‐localization over one or the other phen ligand, the three nuclear movements participate to the flattening of the electronically excited complexes. This leads to negligible energy barriers whatever the ligand X for the first process and significant ligand dependent energy barriers for the formation of the flattened conformers. Born‐Oppenheimer (BO) dynamics simulation of the structural evolution on the T1 PES over 11 ps at 300 K confirms the fast backwards and forwards motion of the phenanthroline within 200–300 fs period and corroborates the presence of metastable C2 structures.
中文翻译：
取代基对2,9-取代菲咯啉铜（I）配合物的光物理性质的影响：理论研究
一系列[Cu（2,9-（X）2 -phen）2 ] +铜（I）配合物（phen = 1,10-phenothroline; X = H，F，Cl，Br，通过密度泛函理论（DFT）和时变（TD-DFT）方法研究了处于基态和激发态的I，Me，CN。随后的Born-Oppenheimer分子动力学用于探索T 1势能面（PES）。T 1和S 1能量分布图，计算了激发分子时由配体变平和Cu-N键对称性断裂引起的简并极小值，以及过渡态（TS）结构和相关的能垒。三个核运动驱动着光物理运动，即协调球非对称呼吸，有据可查的伪Jahn-Teller（PJT）畸变和phen配体的弯曲。这项理论研究揭示了基于势能面最小值和过渡态的静态图像的局限性，以解释此类分子的发光和TADF特性。较小的不对称Cu-N键呼吸伴随着一个或另一个phen配体上的金属-配体-电荷转移重新定位，这三个核运动参与了电子激发复合物的展平。无论用于第一过程的配体X如何，这导致可忽略的能垒以及用于形成扁平构象异构体的明显的依赖于配体的能垒。T形结构演化的Born-Oppenheimer（BO）动力学模拟1个PES在300 K时超过11 ps时，证实了菲咯啉在200–300 fs周期内快速前后运动，并证实了亚稳C 2结构的存在。
更新日期：2020-11-26
中文翻译：
取代基对2,9-取代菲咯啉铜（I）配合物的光物理性质的影响：理论研究
一系列[Cu（2,9-（X）2 -phen）2 ] +铜（I）配合物（phen = 1,10-phenothroline; X = H，F，Cl，Br，通过密度泛函理论（DFT）和时变（TD-DFT）方法研究了处于基态和激发态的I，Me，CN。随后的Born-Oppenheimer分子动力学用于探索T 1势能面（PES）。T 1和S 1能量分布图，计算了激发分子时由配体变平和Cu-N键对称性断裂引起的简并极小值，以及过渡态（TS）结构和相关的能垒。三个核运动驱动着光物理运动，即协调球非对称呼吸，有据可查的伪Jahn-Teller（PJT）畸变和phen配体的弯曲。这项理论研究揭示了基于势能面最小值和过渡态的静态图像的局限性，以解释此类分子的发光和TADF特性。较小的不对称Cu-N键呼吸伴随着一个或另一个phen配体上的金属-配体-电荷转移重新定位，这三个核运动参与了电子激发复合物的展平。无论用于第一过程的配体X如何，这导致可忽略的能垒以及用于形成扁平构象异构体的明显的依赖于配体的能垒。T形结构演化的Born-Oppenheimer（BO）动力学模拟1个PES在300 K时超过11 ps时，证实了菲咯啉在200–300 fs周期内快速前后运动，并证实了亚稳C 2结构的存在。
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