The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies

Michael James Ingleson, Kang Yuan, Rachel J Kahan, Changfeng Si, Amy Williams, Sven Kirschner, Marina Uzelac, Eli Zysman-Colman, M. J. Ingleson*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

The synthesis of a range of brominated-Bn-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr3 with appropriately substituted alkynes via a bromoboration/electrophilic C-H borylation sequence. The brominated-Bn-PAHs were isolated as either the borinic acid or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B2-doped PAHs (with one example having a reduction potential of E1/2 = -0.96 V versus Fc+/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters direct from internal alkynes. Bromoboration/C-H borylation installs useful C-Br units onto the Bn-PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B2-PAH. The resultant D-A-D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.
Original languageEnglish
Pages (from-to)3258-3267
Number of pages10
JournalChemical Science
Volume11
Issue number12
Early online date27 Feb 2020
DOIs
Publication statusPublished - 28 Mar 2020

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