A modular route to boron doped PAHs by combining borylative cyclisation and electrophilic C-H borylation

D. L. Crossley, R. J. Kahan, S. Endres, A. J. Warner, R. A. Smith, J. Cid, J. J. Dunsford, J. E. Jones, I. Vitorica-Yrezabal, M. J. Ingleson

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Abstract

Heteroatom doping into polyaromatic hydrocarbons (PAHs) is a powerful approach for modifying key physical properties, however, there are extremely few modular routes that enable facile formation of B-, B2- and B,N-(specifically not containing direct B-N bonds) doped PAHs despite the growing importance of these materials. Sequential, one pot borylative cyclisation/intramolecular electrophilic C-H borylation of naphthyl-alkynes provides a simple new route to access novel B-, B,N- and B2-doped (PAHs). The initial products, dihydronaphthalene/dihydroquinoline B-mesityl PAHs, were reacted with [Ph3C][BF4]/pyridyl base to form the oxidised B-, and B,N-doped PAHs. However, for B-triisopropylphenyl (Trip) PAH congeners oxidation has to be performed prior to Trip installation due to preferential oxidation of an isopropylaryl moiety to the styrene. This alternative sequence enables access to Trip-B-PAHs and to structurally constrained B and B2-PAHs. Analysis of the solid state structures and optoelectronic properties of these PAHs confirm that frontier orbital energies, extended packing structures, Stokes shift and quantum yields all can be rationally modified using this methodology. The simplicity of this synthetic approach makes it a powerful tool for rapidly generating novel bench stable boron doped PAHs, which is important for facilitating further structure-property relationship studies and the wider utilisation of these materials in optoelectronic applications.
Original languageEnglish
Pages (from-to)7969-7977
Number of pages9
JournalChemical Science
Volume8
Issue number12
Early online date28 Sep 2017
DOIs
Publication statusPublished - Dec 2017
Externally publishedYes

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Boron
Cyclization
Hydrocarbons
Optoelectronic devices
Oxidation
Styrene
Alkynes
Quantum yield
Physical properties
Doping (additives)

Cite this

Crossley, D. L., Kahan, R. J., Endres, S., Warner, A. J., Smith, R. A., Cid, J., ... Ingleson, M. J. (2017). A modular route to boron doped PAHs by combining borylative cyclisation and electrophilic C-H borylation. Chemical Science, 8(12), 7969-7977. https://doi.org/10.1039/c7sc02793a
Crossley, D. L. ; Kahan, R. J. ; Endres, S. ; Warner, A. J. ; Smith, R. A. ; Cid, J. ; Dunsford, J. J. ; Jones, J. E. ; Vitorica-Yrezabal, I. ; Ingleson, M. J. / A modular route to boron doped PAHs by combining borylative cyclisation and electrophilic C-H borylation. In: Chemical Science. 2017 ; Vol. 8, No. 12. pp. 7969-7977.
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Crossley, DL, Kahan, RJ, Endres, S, Warner, AJ, Smith, RA, Cid, J, Dunsford, JJ, Jones, JE, Vitorica-Yrezabal, I & Ingleson, MJ 2017, 'A modular route to boron doped PAHs by combining borylative cyclisation and electrophilic C-H borylation', Chemical Science, vol. 8, no. 12, pp. 7969-7977. https://doi.org/10.1039/c7sc02793a

A modular route to boron doped PAHs by combining borylative cyclisation and electrophilic C-H borylation. / Crossley, D. L.; Kahan, R. J.; Endres, S.; Warner, A. J.; Smith, R. A.; Cid, J.; Dunsford, J. J.; Jones, J. E.; Vitorica-Yrezabal, I.; Ingleson, M. J.

In: Chemical Science, Vol. 8, No. 12, 12.2017, p. 7969-7977.

Research output: Contribution to journalArticle

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T1 - A modular route to boron doped PAHs by combining borylative cyclisation and electrophilic C-H borylation

AU - Crossley, D. L.

AU - Kahan, R. J.

AU - Endres, S.

AU - Warner, A. J.

AU - Smith, R. A.

AU - Cid, J.

AU - Dunsford, J. J.

AU - Jones, J. E.

AU - Vitorica-Yrezabal, I.

AU - Ingleson, M. J.

PY - 2017/12

Y1 - 2017/12

N2 - Heteroatom doping into polyaromatic hydrocarbons (PAHs) is a powerful approach for modifying key physical properties, however, there are extremely few modular routes that enable facile formation of B-, B2- and B,N-(specifically not containing direct B-N bonds) doped PAHs despite the growing importance of these materials. Sequential, one pot borylative cyclisation/intramolecular electrophilic C-H borylation of naphthyl-alkynes provides a simple new route to access novel B-, B,N- and B2-doped (PAHs). The initial products, dihydronaphthalene/dihydroquinoline B-mesityl PAHs, were reacted with [Ph3C][BF4]/pyridyl base to form the oxidised B-, and B,N-doped PAHs. However, for B-triisopropylphenyl (Trip) PAH congeners oxidation has to be performed prior to Trip installation due to preferential oxidation of an isopropylaryl moiety to the styrene. This alternative sequence enables access to Trip-B-PAHs and to structurally constrained B and B2-PAHs. Analysis of the solid state structures and optoelectronic properties of these PAHs confirm that frontier orbital energies, extended packing structures, Stokes shift and quantum yields all can be rationally modified using this methodology. The simplicity of this synthetic approach makes it a powerful tool for rapidly generating novel bench stable boron doped PAHs, which is important for facilitating further structure-property relationship studies and the wider utilisation of these materials in optoelectronic applications.

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SN - 2041-6520

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