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Excited state character of Cibalackrot-type compounds interpreted in terms of Hückel-aromaticity: a rationale for singlet fission chromophore design.

Published version
Peer-reviewed

Type

Article

Change log

Abstract

The exact energies of the lowest singlet and triplet excited states in organic chromophores are crucial to their performance in optoelectronic devices. The possibility of utilizing singlet fission to enhance the performance of photovoltaic devices has resulted in a wide demand for tuneable, stable organic chromophores with wide S1-T1 energy gaps (>1 eV). Cibalackrot-type compounds were recently considered to have favorably positioned excited state energies for singlet fission, and they were found to have a degree of aromaticity in the lowest triplet excited state (T1). This work reports on a revised and deepened theoretical analysis taking into account the excited state Hückel-aromatic (instead of Baird-aromatic) as well as diradical characters, with the aim to design new organic chromophores based on this scaffold in a rational way starting from qualitative theory. We demonstrate that the substituent strategy can effectively adjust the spin distribution on the chromophore and thereby manipulate the excited state energy levels. Additionally, the improved understanding of the aromatic characters enables us to demonstrate a feasible design strategy to vary the excited state energy levels by tuning the number and nature of Hückel-aromatic units in the excited state. Finally, our study elucidates the complications and pitfalls of the excited state aromaticity and antiaromaticity concepts, highlighting that quantitative results from quantum chemical calculations of various aromaticity indices must be linked with qualitative theoretical analysis of the character of the excited states.

Description

Keywords

34 Chemical Sciences, 3406 Physical Chemistry, 3407 Theoretical and Computational Chemistry

Journal Title

Chem Sci

Conference Name

Journal ISSN

2041-6520
2041-6539

Volume Title

12

Publisher

Royal Society of Chemistry (RSC)
Sponsorship
Engineering and Physical Sciences Research Council (EP/S003126/1)
European Commission Horizon 2020 (H2020) Marie Sk?odowska-Curie actions (886066)
Engineering and Physical Sciences Research Council (EP/P007767/1)