A sterically encumbered trans-A₂B-corrole possessing a perylenediimide (PDI) scaffold in close proximity to the macrocycle has been synthesized via a straightforward route. Electronic communication as probed via steady-state absorption or cyclic voltammetry is weak in the ground state, in spite of the corrole ring and PDI being bridged by an o-phenylene unit. The TDDFT excited-state geometry optimization suggests after excitation the interchromophoric distance is markedly reduced, thus enhancing the through-space electronic coupling between the corrole and the PDI. This is corroborated by the strong deviation of the emission spectrum originating from both PDI and corrole in the dyad. Selective excitation of both donor and acceptor units triggers efficient sub-picosecond electron transfer and hole transfer, respectively, followed by fast charge recombination. In comparison to previously studied corrole–PDI dyads, both charge separation and charge recombination occur faster, because of the structural relaxation in the excited state.

中文翻译：

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Corrole-苝二酰亚胺二元组中激发态结构弛豫驱动的高效电子转移

通过简单的途径合成了具有紧邻大环的苝二酰亚胺（PDI）支架的空间阻碍的反式-A ₂ B-咔咯。尽管咔咯环和 PDI 通过邻亚苯基单元桥联，但通过稳态吸收或循环伏安法探测的电子通讯在基态下较弱。 TDDFT 激发态几何优化表明，激发后发色团间距离显着减小，从而增强了corrole 和PDI 之间的全空间电子耦合。源自二元体中 PDI 和 Corrole 的发射光谱的强烈偏差证实了这一点。供体和受体单元的选择性激发分别触发有效的亚皮秒电子转移和空穴转移，然后进行快速电荷复合。与之前研究的corrole-PDI二元组相比，由于激发态的结构弛豫，电荷分离和电荷重组发生得更快。