Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups
Zuolun Zhang, Robert M. Edkins, Jorn Nitsch, Katharina Edkins, Andreas Steffen, Lauren E. Longobardi, Douglas W. Stephan, Christoph Lambert, Todd B. Marder
Three compounds with phenyl (1), 4-tert-butylphenyl (2) and 4-N,N-diphenylaminophenyl (3) groups attached to bis(fluoromesityl)boryl ((FMes)2B) through B–C bonds have been prepared. The restricted rotation about the B–C bonds of boron-bonded aryl rings in solution has been studied by variable-temperature 19F NMR spectroscopy, and through-space F–F coupling has been observed for 3 at low temperature. Steric congestion inhibits binding of 1 by Lewis bases DABCO and tBu3P and the activation of H2 in their presence. Photophysical and electrochemical studies have been carried out on 2, 3, and an analogue of 3 containing a bis(mesityl)boryl ((Mes)2B) group, namely 4. Both 2 and 3 show bright emission in nonpolar solvents and in the solid-state, very strong electron-accepting ability as measured by cyclic voltammetry, and good air-stability. In addition, 2 displayed unusually long-lived emission (τ = 2.47 s) in 2-MeTHF at 77 K. The much stronger acceptor strength of (FMes)2B than (Mes)2B leads to significantly red-shifted emission in solution and the solid state, stronger emission solvatochromism, and significantly lower reduction potentials. Theoretical calculations confirm that 2 and 3 tend to form highly twisted excited states with good conjugation between one FMes group and the boron atom, which correlate well with their blue-shifted solid-state emissions and low kr values in solution.
https://doi.org/10.1039/C4SC02410A
10.1039/C4SC02410A
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Solid Chemistry 100%
Aqueous Solution Chemistry 100%
Electron Particle Chemistry 66%
Group Chemistry 66%
Reaction Temperature Chemistry 66%
Chemical Bond Chemistry 66%
Boron Atom Chemistry 66%
Boryl Group Chemistry 66%
Zhang, Z., Edkins, R. M., Nitsch, J., Edkins, K., Steffen, A., Longobardi, L. E., Stephan, D. W., Lambert, C., & Marder, T. B. (2014). Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups. Chemical Science, 6(1), 308-321. https://doi.org/10.1039/C4SC02410A
Zhang, Zuolun ; Edkins, Robert M. ; Nitsch, Jorn et al. / Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups. In: Chemical Science. 2014 ; Vol. 6, No. 1. pp. 308-321.
@article{18f172354bc842f09ca5f0eae141c475,
title = "Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups",
abstract = "Three compounds with phenyl (1), 4-tert-butylphenyl (2) and 4-N,N-diphenylaminophenyl (3) groups attached to bis(fluoromesityl)boryl ((FMes)2B) through B–C bonds have been prepared. The restricted rotation about the B–C bonds of boron-bonded aryl rings in solution has been studied by variable-temperature 19F NMR spectroscopy, and through-space F–F coupling has been observed for 3 at low temperature. Steric congestion inhibits binding of 1 by Lewis bases DABCO and tBu3P and the activation of H2 in their presence. Photophysical and electrochemical studies have been carried out on 2, 3, and an analogue of 3 containing a bis(mesityl)boryl ((Mes)2B) group, namely 4. Both 2 and 3 show bright emission in nonpolar solvents and in the solid-state, very strong electron-accepting ability as measured by cyclic voltammetry, and good air-stability. In addition, 2 displayed unusually long-lived emission (τ = 2.47 s) in 2-MeTHF at 77 K. The much stronger acceptor strength of (FMes)2B than (Mes)2B leads to significantly red-shifted emission in solution and the solid state, stronger emission solvatochromism, and significantly lower reduction potentials. Theoretical calculations confirm that 2 and 3 tend to form highly twisted excited states with good conjugation between one FMes group and the boron atom, which correlate well with their blue-shifted solid-state emissions and low kr values in solution.",
author = "Zuolun Zhang and Edkins, {Robert M.} and Jorn Nitsch and Katharina Edkins and Andreas Steffen and Longobardi, {Lauren E.} and Stephan, {Douglas W.} and Christoph Lambert and Marder, {Todd B.}",
doi = "10.1039/C4SC02410A",
publisher = "Royal Society of Chemistry",
Zhang, Z, Edkins, RM, Nitsch, J, Edkins, K, Steffen, A, Longobardi, LE, Stephan, DW, Lambert, C & Marder, TB 2014, 'Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups', Chemical Science, vol. 6, no. 1, pp. 308-321. https://doi.org/10.1039/C4SC02410A
Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups. / Zhang, Zuolun; Edkins, Robert M.; Nitsch, Jorn et al.
In: Chemical Science, Vol. 6, No. 1, 01.10.2014, p. 308-321.
T1 - Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups
AU - Zhang, Zuolun
AU - Edkins, Robert M.
AU - Nitsch, Jorn
AU - Edkins, Katharina
AU - Steffen, Andreas
AU - Longobardi, Lauren E.
AU - Stephan, Douglas W.
AU - Lambert, Christoph
AU - Marder, Todd B.
N2 - Three compounds with phenyl (1), 4-tert-butylphenyl (2) and 4-N,N-diphenylaminophenyl (3) groups attached to bis(fluoromesityl)boryl ((FMes)2B) through B–C bonds have been prepared. The restricted rotation about the B–C bonds of boron-bonded aryl rings in solution has been studied by variable-temperature 19F NMR spectroscopy, and through-space F–F coupling has been observed for 3 at low temperature. Steric congestion inhibits binding of 1 by Lewis bases DABCO and tBu3P and the activation of H2 in their presence. Photophysical and electrochemical studies have been carried out on 2, 3, and an analogue of 3 containing a bis(mesityl)boryl ((Mes)2B) group, namely 4. Both 2 and 3 show bright emission in nonpolar solvents and in the solid-state, very strong electron-accepting ability as measured by cyclic voltammetry, and good air-stability. In addition, 2 displayed unusually long-lived emission (τ = 2.47 s) in 2-MeTHF at 77 K. The much stronger acceptor strength of (FMes)2B than (Mes)2B leads to significantly red-shifted emission in solution and the solid state, stronger emission solvatochromism, and significantly lower reduction potentials. Theoretical calculations confirm that 2 and 3 tend to form highly twisted excited states with good conjugation between one FMes group and the boron atom, which correlate well with their blue-shifted solid-state emissions and low kr values in solution.
AB - Three compounds with phenyl (1), 4-tert-butylphenyl (2) and 4-N,N-diphenylaminophenyl (3) groups attached to bis(fluoromesityl)boryl ((FMes)2B) through B–C bonds have been prepared. The restricted rotation about the B–C bonds of boron-bonded aryl rings in solution has been studied by variable-temperature 19F NMR spectroscopy, and through-space F–F coupling has been observed for 3 at low temperature. Steric congestion inhibits binding of 1 by Lewis bases DABCO and tBu3P and the activation of H2 in their presence. Photophysical and electrochemical studies have been carried out on 2, 3, and an analogue of 3 containing a bis(mesityl)boryl ((Mes)2B) group, namely 4. Both 2 and 3 show bright emission in nonpolar solvents and in the solid-state, very strong electron-accepting ability as measured by cyclic voltammetry, and good air-stability. In addition, 2 displayed unusually long-lived emission (τ = 2.47 s) in 2-MeTHF at 77 K. The much stronger acceptor strength of (FMes)2B than (Mes)2B leads to significantly red-shifted emission in solution and the solid state, stronger emission solvatochromism, and significantly lower reduction potentials. Theoretical calculations confirm that 2 and 3 tend to form highly twisted excited states with good conjugation between one FMes group and the boron atom, which correlate well with their blue-shifted solid-state emissions and low kr values in solution.
U2 - 10.1039/C4SC02410A
DO - 10.1039/C4SC02410A
JO - Chemical Science
JF - Chemical Science
Zhang Z, Edkins RM, Nitsch J, Edkins K, Steffen A, Longobardi LE et al. Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups. Chemical Science. 2014 Oct 1;6(1):308-321. doi: 10.1039/C4SC02410A