Tuning the Inter-Chromophore Electronic Coupling in Perylene Diimide Dimers with Rigid Covalent Linkers

Tuning the Inter-Chromophore Electronic Coupling in Perylene Diimide Dimers with Rigid Covalent Linkers

The organic multi-chromophore system has been increasingly attractive due to the potential optoelectronic applications. The inter-chromophore electronic coupling (EC), i.e., <i>J</i><sub>Coul</sub> and <i>J</i><sub>CT</sub>, plays a critical role in de...

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Bibliographic Details
Main Authors: Guo Yu, Yixuan Gao, Yonghang Li, Yiran Tian, Xiaoyu Zhang, Yandong Han, Jinsheng Song, Wensheng Yang, Xiaonan Ma
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Molecules
Subjects:
perylene diimide
covalent dimer
electronic coupling
structural relaxation
excited state
molecular designing
Online Access:https://www.mdpi.com/1420-3049/30/12/2513
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Summary:The organic multi-chromophore system has been increasingly attractive due to the potential optoelectronic applications. The inter-chromophore electronic coupling (EC), i.e., <i>J</i><sub>Coul</sub> and <i>J</i><sub>CT</sub>, plays a critical role in determining the relaxation path of the excited state. However, the molecular designing strategy for effective tuning of inter-chromophore EC is still challenging. In this computational work, we designed a series of perylene diimides (PDI) covalent dimers with rigid linking cores containing thiophene (Th) or phenyl (Ph) fragments and performed corresponding theoretical investigation to analyze the inter-PDI electronic coupling. Vibrational analysis indicated that the minimized excited state structural relaxation (ES-SR) can ensure the rigid inter-PDI geometry pre-defined by the topological characteristic of linking cores, leading to comparable |<i>J</i><sub>Coul</sub>| on S<sub>0</sub> and S<sub>1</sub> states. The saddle-shaped linking cores allow collaborative tuning of inter-PDI dihedral (<i>α</i>) and slipping (<i>θ</i>) angles, leading to effective tuning of inter-PDI |<i>J</i><sub>Coul</sub>| = 0–1000 cm<sup>−1</sup>. Our work provides a new molecular designing strategy for effective tuning of inter-chromophore EC for organic chromophores. By using a rigid inter-chromophore structure, the ignorable ES-SR allows simplified molecular designing without considering the plausible geometric difference between S<sub>1</sub> and S<sub>0</sub> states, which might be useful for future applications in organic optoelectronics.
ISSN:1420-3049

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