Synthetic, structural, photophysical and computational studies on 2-arylethynyl-1,3,2-diazaboroles

New 2-arylalkynyl benzo-1,3,2-diazaboroles,2-(4'-XC6H4C C)-1,3-Et-2-1,3,2-N2BC6H4(X= Me 2; MeO 3; MeS 4; Me2N 5), were prepared from B-bromodiazaborole, 2-Br-1,3-Et-2-1,3,2-N2BC6H4, with the appropriate lithiated arylacetylene, ArC CLi. Molecular structures of 2, 3 and 5 were determined by X-ray diffraction studies. UV-vis and luminescence spectroscopic studies on these diazaboroles reveal intense blue/violet fluorescence with very large quantum yields of 0.89-0.99 for 2-5. The experimental findings were complemented by DFT and TD-DFT calculations. The Stokes shift of only 2600 cm(-1) for 5, compared to Stokes shifts in the range of 5900-7300 cm(-1) for 1-4, is partly explained by the different electronic structures found in 5 compared to 1-4 (X = H). The HOMO is mainly located on the aryl group in 5 and on the diazaborolyl group in 1-4 whereas the LUMOs are largely aryl in character for all compounds. Thus, in contrast to other conjugated systems containing three-coordinate boron centers such as B(Mes)(2), (Mes=2,4,6-Me3C6H2), in which the boron serves as a pi-acceptor, the 10-pi electron benzodiazaborole moiety appears to function as a pi-donor moiety.