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Bending versus Twisting Acenes – A Computational Study

Polycyclic aromatic hydrocarbons (PAHs) are widely used in organic electronic devices. The electronic, magnetic, and optical properties of PAHs can be tuned by structural modifications to the aromatic backbone to introduce an inherent distortion from planarity, such as bending or twisting. However,...

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Detalles Bibliográficos
Autores principales: Armon, Amit Manor, Bedi, Anjan, Borin, Veniamin, Schapiro, Igor, Gidron, Ori
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597036/
https://www.ncbi.nlm.nih.gov/pubmed/34819798
http://dx.doi.org/10.1002/ejoc.202100865
Descripción
Sumario:Polycyclic aromatic hydrocarbons (PAHs) are widely used in organic electronic devices. The electronic, magnetic, and optical properties of PAHs can be tuned by structural modifications to the aromatic backbone to introduce an inherent distortion from planarity, such as bending or twisting. However, it remains difficult to isolate and control the effects of such distortions. Here, we sought to understand how backbone twisting and bending affect the electronic properties of acenes, as models for larger PAHs. We found that, even when highly distorted from planarity (30° per ring), acenes maintain their aromatic character and π orbital delocalization with minor mixing of the σ and π orbitals. In addition, the energy gap between the HOMO and LUMO decreases with increasing twist, while the gap is hardly affected by bending, since the energy of both orbitals increase to a similar extent. For bent acenes in the triplet state, the spin becomes more localized with increasing bend, whereas twisting produces an evenly distributed spin delocalization. These findings can guide the synthesis of PAHs with tailored properties.