C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry

Weber L, Kahlert J, Brockhinke R, Böhling L, Halama J, Brockhinke A, Stammler H-G, Neumann B, Nervi C, Harder RA, Fox MA (2013)
Journal of the Chemical Society. Dalton Transactions 42(30): 10982-10996.

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Abstract
Six new C,C'-bis(benzodiazaborolyl)dicarba-closo-dodecaboranes, 1,A-R-2-1,A-C2B10H10, where R represents the group 2-(1,3-Et-2-1,3,2-N2BC6H4) or 2-(1,3-Ph-2-1,3,2-N2BC6H4) and A is 2, 7 or 12, were synthesized from o-, m-, and p-dicarbadodecaboranes (carboranes) by lithiation and subsequent treatment with the respective 2-bromo-1,3,2-benzodiazaboroles. UV-visible and fluorescence spectra of all carboranes display low energy charge transfer emissions. While such emissions with Stokes shifts between 17 330 and 21 290 cm(-1) are typical for C,C'-bis(aryl)-ortho-carboranes, the observed low-energy emissions with Stokes shifts between 8320 and 15 170 cm(-1) for the meta-and para-isomers are unusual as high-energy emissions are typical for meta- and para-dicarbadodecaboranes. Fluorescence quantum yields (phi(F)) for the novel 1,7- and 1,12-bis(benzodiazaborolyl)-carboranes depend on the substituents at the nitrogen atoms of the heterocycle. Thus, the para-carborane with N-ethyl substituents 1,12-(1',3'-Et-2-1',3',2'-N2BC6H4)(2)-1,12-C2B10H10 has phi(F) value of 41% in cyclohexane solution and only of 9% in the solid state, whereas the analogous 1,12-(1',3'-Ph-2-1',3',2'-N2BC6H4)(2)-1,12-C2B10H10 shows quantum yields of 3% in cyclohexane solution and 72% in the solid state. X-ray crystallographic, computational and cyclic voltammetry studies for these carboranes are also presented.
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Weber L, Kahlert J, Brockhinke R, et al. C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry. Journal of the Chemical Society. Dalton Transactions. 2013;42(30):10982-10996.
Weber, L., Kahlert, J., Brockhinke, R., Böhling, L., Halama, J., Brockhinke, A., Stammler, H. - G., et al. (2013). C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry. Journal of the Chemical Society. Dalton Transactions, 42(30), 10982-10996.
Weber, L., Kahlert, J., Brockhinke, R., Böhling, L., Halama, J., Brockhinke, A., Stammler, H. - G., Neumann, B., Nervi, C., Harder, R. A., et al. (2013). C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry. Journal of the Chemical Society. Dalton Transactions 42, 10982-10996.
Weber, L., et al., 2013. C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry. Journal of the Chemical Society. Dalton Transactions, 42(30), p 10982-10996.
L. Weber, et al., “C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry”, Journal of the Chemical Society. Dalton Transactions, vol. 42, 2013, pp. 10982-10996.
Weber, L., Kahlert, J., Brockhinke, R., Böhling, L., Halama, J., Brockhinke, A., Stammler, H.-G., Neumann, B., Nervi, C., Harder, R.A., Fox, M.A.: C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry. Journal of the Chemical Society. Dalton Transactions. 42, 10982-10996 (2013).
Weber, Lothar, Kahlert, Jan, Brockhinke, Regina, Böhling, Lena, Halama, Johannes, Brockhinke, Andreas, Stammler, Hans-Georg, Neumann, Beate, Nervi, Carlo, Harder, Rachel A., and Fox, Mark A. “C,C '-Bis(benzodiazaborolyl)dicarba-closo-dodecaboranes: Synthesis, structures, photophysics and electrochemistry”. Journal of the Chemical Society. Dalton Transactions 42.30 (2013): 10982-10996.
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