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Excited-State (Anti)Aromaticity Explains Why Azulene Disobeys Kasha's Rule
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- Dunlop, David (författare)
- Czech Acad Sci, Inst Organ Chem & Biochem, Prague 6, Czech Republic.; Charles Univ Prague, Fac Sci, Dept Inorgan Chem, Prague 2, Czech Republic.
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- Ludvikova, Lucie (författare)
- Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo náměstí 542/2, Prague 6 160 00, Czech Republic.
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- Banerjee, Ambar (författare)
- Uppsala universitet,Institutionen för fysik och astronomi
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- Ottosson, Henrik (författare)
- Uppsala universitet,Institutionen för kemi - Ångström
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- Slanina, Tomas (författare)
- Czech Acad Sci, Inst Organ Chem & Biochem, Prague 6, Czech Republic.
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Czech Acad Sci, Inst Organ Chem & Biochem, Prague 6, Czech Republic; Charles Univ Prague, Fac Sci, Dept Inorgan Chem, Prague 2, Czech Republic. Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo náměstí 542/2, Prague 6 160 00, Czech Republic. (creator_code:org_t)
- American Chemical Society (ACS), 2023
- 2023
- Engelska.
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 145:39, s. 21569-21575
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https://uu.diva-port... (primary) (Raw object)
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- Fluorescence exclusively occurs from the lowest excited state of a given multiplicity according to Kasha's rule. However, this rule is not obeyed by a handful of anti-Kasha fluorophores whose underlying mechanism is still understood merely on a phenomenological basis. This lack of understanding prevents the rational design and property-tuning of anti-Kasha fluorophores. Here, we propose a model explaining the photophysical properties of an archetypal anti-Kasha fluorophore, azulene, based on its ground- and excited-state (anti)aromaticity. We derived our model from a detailed analysis of the electronic structure of the ground singlet, first excited triplet, and quintet states and of the first and second excited singlet states using the perturbational molecular orbital theory and quantum-chemical aromaticity indices. Our model reveals that the anti-Kasha properties of azulene and its derivatives result from (i) the contrasting (anti)aromaticity of its first and second singlet excited states (S-1 and S-2, respectively) and (ii) an easily accessible antiaromaticity relief pathway of the S-1 state. This explanation of the fundamental cause of anti-Kasha behavior may pave the way for new classes of anti-Kasha fluorophores and materials with long-lived, high-energy excited states.
Ämnesord
- NATURVETENSKAP -- Kemi -- Materialkemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Materials Chemistry (hsv//eng)
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