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

doi:10.1039/C9SC05404A

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 journal › Article › peer-review

Abstract

The synthesis of a range of brominated-B_n-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-B_n-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 E_1/2 = -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 B_n-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 language	English
Pages (from-to)	3258-3267
Number of pages	10
Journal	Chemical Science
Volume	11
Issue number	12
Early online date	27 Feb 2020
DOIs	https://doi.org/10.1039/C9SC05404A
Publication status	Published - 28 Mar 2020

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Yuan_2020_CS_Brominated-boron-doped_CC
Copyright © 2020 The Author(s). Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Final published version, 1.25 MBLicence: CC BY

TADF Emitters for OLEDs - Eli Zysman: TADF Emitters for OLEDs
Zysman-Colman, E. (PI)
EPSRC
1/03/17 → 31/03/21
Project: Standard

The Synthesis of Brominated-Boron-Doped PAHs by Alkyne 1,1- Bromoboration: Mechanistic and Functionalisation Studies (dataset)
Yuan, K. (Creator), Kahan, R. J. (Creator), Si, C. (Creator), Williams, A. (Creator), Kirschnera, S. (Creator), Uzelac, M. (Creator), Zysman-Colman, E. (Creator) & Ingleson, M. J. (Creator), University of St Andrews, 2020
DOI: 10.17630/3764e0e8-38dc-42b9-a77d-152eabdfd4db
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title = "The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies",

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.",

author = "Ingleson, {Michael James} and Kang Yuan and Kahan, {Rachel J} and Changfeng Si and Amy Williams and Sven Kirschner and Marina Uzelac and Eli Zysman-Colman and Ingleson, {M. J.}",

note = "The research leading to these results has received funding from the European Research Council under the Horizon 2020 Research and Innovation Program (Grant no. 769599), the Leverhulme Trust (RPG-2014-340) and the EPSRC (EP/P010482/1). C. Si thanks the China Scholarship Council (201806890001).",

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language = "English",

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T2 - mechanistic and functionalisation studies

AU - Ingleson, Michael James

AU - Yuan, Kang

AU - Kahan, Rachel J

AU - Si, Changfeng

AU - Williams, Amy

AU - Kirschner, Sven

AU - Uzelac, Marina

AU - Zysman-Colman, Eli

AU - Ingleson, M. J.

N1 - The research leading to these results has received funding from the European Research Council under the Horizon 2020 Research and Innovation Program (Grant no. 769599), the Leverhulme Trust (RPG-2014-340) and the EPSRC (EP/P010482/1). C. Si thanks the China Scholarship Council (201806890001).

PY - 2020/3/28

Y1 - 2020/3/28

N2 - 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.

AB - 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.

U2 - 10.1039/C9SC05404A

DO - 10.1039/C9SC05404A

M3 - Article

SN - 2041-6520

VL - 11

SP - 3258

EP - 3267

JO - Chemical Science

JF - Chemical Science

IS - 12

ER -

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

Abstract

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Datasets

The Synthesis of Brominated-Boron-Doped PAHs by Alkyne 1,1- Bromoboration: Mechanistic and Functionalisation Studies (dataset)

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