Cyclopropyl Group: An Excited-State Aromaticity Indicator?Show others and affiliations
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 55, p. 13684-13695Article in journal (Refereed) Published
Abstract [en]
The cyclopropyl (cPr) group, which is a well-known probe for detecting radical character at atoms to which it is connected, is tested as an indicator for aromaticity in the first ππ* triplet and singlet excited states (T1 and S1). Baird's rule says that the π-electron counts for aromaticity and antiaromaticity in the T1 and S1 states are opposite to Hückel's rule in the ground state (S0). Our hypothesis is that the cPr group, as a result of Baird's rule, will remain closed when attached to an excited-state aromatic ring, enabling it to be used as an indicator to distinguish excited-state aromatic rings from excited-state antiaromatic and nonaromatic rings. Quantum chemical calculations and photoreactivity experiments support our hypothesis; calculated aromaticity indices reveal that openings of cPr substituents on [4n]annulenes ruin the excited-state aromaticity in energetically unfavorable processes. Yet, polycyclic compounds influenced by excited-state aromaticity (e.g., biphenylene), as well as 4nπ-electron heterocycles with two or more heteroatoms represent limitations.
Place, publisher, year, edition, pages
Wiley-VCH Verlag , 2017. Vol. 23, no 55, p. 13684-13695
Keywords [en]
aromaticity, density functional calculations, electronic structures, photochemistry, small-ring compounds, Aromatic compounds, Aromatization, Density functional theory, Electronic structure, Ground state, Photochemical reactions, Quantum chemistry, Quantum theory, Antiaromaticity, Aromaticities, Aromaticity indices, Cyclopropyl group, Polycyclic compounds, Quantum chemical calculations, Singlet excited state, Small rings, Excited states
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:ri:diva-57307DOI: 10.1002/chem.201701404Scopus ID: 2-s2.0-85028626815OAI: oai:DiVA.org:ri-57307DiVA, id: diva2:1616694
Note
Funding details: Vetenskapsrådet, VR, 2015–04538; Funding text 1: We are grateful to the Erasmus Mundus EXPERTS III program for PhD scholarship to R.A., the Wenner–Gren Foundations, and the Swedish Research Council (grant 2015–04538) for financial support. Moreover, H.O. thanks Joakim Bergman and Per-Ola Norrby, AstraZeneca Gothenburg, for stimulating discussions on the cyclopropyl group in pharmaceutical chemistry. We also thank the SNIC (Swedish National Infrastructure for computing) through NSC (National Supercomputer Center), Linkçping, and UPPMAX, Sweden for generous allotment of computer time.
2021-12-032021-12-032021-12-03Bibliographically approved