Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes

Weber L, Eickhoff D, Werner V, Böhling L, Schwedler S, Chrostowska A, Dargelos A, Maciejczyk M, Stammler H-G, Neumann B (2011)
Journal of the Chemical Society. Dalton transactions 40(17): 4434-4446.

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Abstract
A series of diphenylacetylenes with one 1,3,2-benzodiazaborolyl end group (BDB) and a second end group X (X = H, OMe, NMe2, SMe, CN and BDB) were synthesized using established 1,3,2-benzodiazaborole methodologies. The 1,3,2-benzodiazaborolyldiphenylacetylenes with X = p-H (4), p-OMe (5), p-NMe2 (6), p-SMe (7) and p-CN (8) end groups are functionalized with cyano groups at the central ring in an ortho-position to the triple bond. Molecular structures of 2, 3, 5, 6 and 7 were determined by X-ray diffraction. These borylated systems show intense blue luminescence in cyclohexane, toluene, chloroform, dichloromethane and tetrahydrofuran, whereas green luminescence was observed in acetonitrile solutions. Thereby Stokes shifts in the range 1700-8600 cm(-1) and quantum yields of 0.60-1.00 were observed in cyclohexane solutions. The absorption maxima (308-380 nm) are well reproduced by TD-DFT computations (B3LYP/G-311G(d, p)) and arise from strong HOMO-LUMO transitions. The LUMOs in all the molecules under study are mainly located on the diphenylacetylene bridge, while with the exception of the dimethylamino derivative 6, the HOMO is largely benzodiazaborolyl in character. Thus, the S1 <- S0 absorption bands are assigned to pi(diazaborolyl)-pi*(diphenylacetylene) transitions. In contrast to this, in compound 6 the HOMO is mainly represented by the terminal dimethylaminophenyl unit. While calculated ground state dipole moments mu(g) are small (1.1-7.5 D), experimentally determined changes of the dipole moments upon excitation are large (14.8-19.7 D) and reflect a significant charge transfer upon excitation. NLO activities of the rod-structured compounds 2, 4, 6 and 8 are indicated by calculated static first-order hyperpolarizabilities beta up to 76.8 x 10(-30) esu.
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Weber L, Eickhoff D, Werner V, et al. Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes. Journal of the Chemical Society. Dalton transactions. 2011;40(17):4434-4446.
Weber, L., Eickhoff, D., Werner, V., Böhling, L., Schwedler, S., Chrostowska, A., Dargelos, A., et al. (2011). Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes. Journal of the Chemical Society. Dalton transactions, 40(17), 4434-4446.
Weber, L., Eickhoff, D., Werner, V., Böhling, L., Schwedler, S., Chrostowska, A., Dargelos, A., Maciejczyk, M., Stammler, H. - G., and Neumann, B. (2011). Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes. Journal of the Chemical Society. Dalton transactions 40, 4434-4446.
Weber, L., et al., 2011. Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes. Journal of the Chemical Society. Dalton transactions, 40(17), p 4434-4446.
L. Weber, et al., “Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes”, Journal of the Chemical Society. Dalton transactions, vol. 40, 2011, pp. 4434-4446.
Weber, L., Eickhoff, D., Werner, V., Böhling, L., Schwedler, S., Chrostowska, A., Dargelos, A., Maciejczyk, M., Stammler, H.-G., Neumann, B.: Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes. Journal of the Chemical Society. Dalton transactions. 40, 4434-4446 (2011).
Weber, Lothar, Eickhoff, Daniel, Werner, Vanessa, Böhling, Lena, Schwedler, Stefanie, Chrostowska, Anna, Dargelos, Alain, Maciejczyk, Malgorzata, Stammler, Hans-Georg, and Neumann, Beate. “Syntheses, crystal structures, photophysical and theoretical studies of 1,3,2-benzodiazaborolyl-functionalized diphenylacetylenes”. Journal of the Chemical Society. Dalton transactions 40.17 (2011): 4434-4446.
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Data provided by Europe PubMed Central.

On the ambiguity of 1,3,2-benzodiazaboroles as donor/acceptor functionalities in luminescent molecules.
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Electrochemical and spectroelectrochemical studies of C-benzodiazaborolyl-ortho-carboranes.
Weber L, Kahlert J, Bohling L, Brockhinke A, Stammler HG, Neumann B, Harder RA, Low PJ, Fox MA., Dalton Trans 42(6), 2013
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Diazaborolyl-boryl push-pull systems with ethynylene-arylene bridges as 'turn-on' fluoride sensors.
Weber L, Eickhoff D, Kahlert J, Bohling L, Brockhinke A, Stammler HG, Neumann B, Fox MA., Dalton Trans 41(34), 2012
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Syntheses of rod-shaped fluorescent 1,3,2-benzodiazaboroles with phosphonium, and phosphane chalcogenide acceptor functions.
Weber L, Kuhtz H, Bohling L, Brockhinke A, Chrostowska A, Dargelos A, Maziere A, Stammler HG, Neumann B., Dalton Trans 41(34), 2012
PMID: 22797550
Luminescence properties of C-diazaborolyl-ortho-carboranes as donor-acceptor systems.
Weber L, Kahlert J, Brockhinke R, Bohling L, Brockhinke A, Stammler HG, Neumann B, Harder RA, Fox MA., Chemistry 18(27), 2012
PMID: 22623079
Experimental and theoretical studies on organic D-π-A systems containing three-coordinate boron moieties as both π-donor and π-acceptor.
Weber L, Eickhoff D, Marder TB, Fox MA, Low PJ, Dwyer AD, Tozer DJ, Schwedler S, Brockhinke A, Stammler HG, Neumann B., Chemistry 18(5), 2012
PMID: 22213064

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