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Triplet state homoaromaticity : concept, computational validation and experimental relevance

(2018) CHEMICAL SCIENCE. 9(12). p.3165-3176
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Organization
Abstract
Cyclic conjugation that occurs through-space and leads to aromatic properties is called homoaromaticity. Here we formulate the homoaromaticity concept for the triplet excited state (T1) based on Baird's 4n rule and validate it through extensive quantum-chemical calculations on a range of different species (neutral, cationic and anionic). By comparison to well-known ground state homoaromatic molecules we reveal that five of the investigated compounds show strong T1 homoaromaticity, four show weak homoaromaticity and two are non-aromatic. Two of the compounds have previously been identified as excited state intermediates in photochemical reactions and our calculations indicate that they are also homoaromatic in the first singlet excited state. Homoaromaticity should therefore have broad implications in photochemistry. We further demonstrate this by computational design of a photomechanical “lever” that is powered by relief of homoantiaromatic destabilization in the first singlet excited state.
Keywords
INDEPENDENT CHEMICAL-SHIFTS, POLYCYCLIC AROMATIC-HYDROCARBONS, MOLECULAR-ORBITAL METHODS, MULTICENTER BOND INDEXES, INDUCED MAGNETIC-FIELD, AB-INITIO CALCULATION, ACID-BASE BEHAVIOR, EXCITED-STATE, ORGANIC-PHOTOCHEMISTRY, DELOCALIZATION INDEXES

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Chicago
Jorner, Kjell, Burkhard O Jahn, Patrick Bultinck, and Henrik Ottosson. 2018. “Triplet State Homoaromaticity : Concept, Computational Validation and Experimental Relevance.” Chemical Science 9 (12): 3165–3176.
APA
Jorner, K., Jahn, B. O., Bultinck, P., & Ottosson, H. (2018). Triplet state homoaromaticity : concept, computational validation and experimental relevance. CHEMICAL SCIENCE, 9(12), 3165–3176.
Vancouver
1.
Jorner K, Jahn BO, Bultinck P, Ottosson H. Triplet state homoaromaticity : concept, computational validation and experimental relevance. CHEMICAL SCIENCE. 2018;9(12):3165–76.
MLA
Jorner, Kjell, Burkhard O Jahn, Patrick Bultinck, et al. “Triplet State Homoaromaticity : Concept, Computational Validation and Experimental Relevance.” CHEMICAL SCIENCE 9.12 (2018): 3165–3176. Print.
@article{8557692,
  abstract     = {Cyclic conjugation that occurs through-space and leads to aromatic properties is called homoaromaticity. Here we formulate the homoaromaticity concept for the triplet excited state (T1) based on Baird's 4n rule and validate it through extensive quantum-chemical calculations on a range of different species (neutral, cationic and anionic). By comparison to well-known ground state homoaromatic molecules we reveal that five of the investigated compounds show strong T1 homoaromaticity, four show weak homoaromaticity and two are non-aromatic. Two of the compounds have previously been identified as excited state intermediates in photochemical reactions and our calculations indicate that they are also homoaromatic in the first singlet excited state. Homoaromaticity should therefore have broad implications in photochemistry. We further demonstrate this by computational design of a photomechanical “lever” that is powered by relief of homoantiaromatic destabilization in the first singlet excited state.},
  author       = {Jorner, Kjell and Jahn, Burkhard O and Bultinck, Patrick and Ottosson, Henrik},
  issn         = {2041-6520},
  journal      = {CHEMICAL SCIENCE},
  keywords     = {INDEPENDENT CHEMICAL-SHIFTS,POLYCYCLIC AROMATIC-HYDROCARBONS,MOLECULAR-ORBITAL METHODS,MULTICENTER BOND INDEXES,INDUCED MAGNETIC-FIELD,AB-INITIO CALCULATION,ACID-BASE BEHAVIOR,EXCITED-STATE,ORGANIC-PHOTOCHEMISTRY,DELOCALIZATION INDEXES},
  language     = {eng},
  number       = {12},
  pages        = {3165--3176},
  title        = {Triplet state homoaromaticity : concept, computational validation and experimental relevance},
  url          = {http://dx.doi.org/10.1039/c7sc05009g},
  volume       = {9},
  year         = {2018},
}

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