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

New 2-arylalkynyl benzo-1,3,2-diazaboroles, 2-(4'-XC(6)H(4)C[triple bond, length as m-dash]C)-1,3-Et(2)-1,3,2-N(2)BC(6)H(4) (X =Me ; MeO ; MeS ; Me(2)N ), were prepared from B-bromodiazaborole, 2-Br-1,3-Et(2)-1,3,2-N(2)BC(6)H(4), with the appropriate lithiated arylacetylene, ArC[triple bond, length as m-dash]CLi. Molecular structures of , and 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 . The experimental findings were complemented by DFT and TD-DFT calculations. The Stokes shift of only 2600 cm(-1) for , compared to Stokes shifts in the range of 5900-7300 cm(-1) for , is partly explained by the different electronic structures found in compared to (X = H). The HOMO is mainly located on the aryl group in and on the diazaborolyl group in 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-Me(3)C(6)H(2)), in which the boron serves as a pi-acceptor, the 10-pi electron benzodiazaborole moiety appears to function as a pi-donor moiety.