Syntheses of rod-shaped fluorescent 1,3,2-benzodiazaboroles with phosphonium, and phosphane chalcogenide acceptor functionsElectronic supplementary information (ESI) available: Tables of atomic coordinates for [B3LYP/6-311G(d,p)] optimized geometries, values of total energies and ionization energies (IEs) of 2-11. CCDC 873268-873276. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt30666b

A series of 1,4-phenylenes X-C 6 H 4 -BDB with a 1,3,2-benzodiazaborolyl (BDB) and a phosphorus based end group [X = PPh 2 ( 2 ), P(O)Ph 2 ( 3 ), P(S)Ph 2 ( 4 ), P(Se)Ph 2 ( 5 ), P(AuCl)Ph 2 ( 6 ) and P(Me)Ph 2 ( 7 )] as well as 2-(2)thienyl-1,3,2-benzodiazaboroles with a second end group X [X = PPh 2 ( 8 ), P(S)Ph 2 ( 9 ), P(Se)Ph 2 ( 10 ) and P(Me)Ph 2 ( 11 )] in the 5 position were synthesised using established methodologies. Molecular structures of 2-9 and 11 were determined by X-ray diffraction. Compounds 3 , 4 , 6 , 7 , 9 and 11 show intense blue luminescence in cyclohexane, toluene, chloroform, dichloromethane and tetrahydrofuran with pronounced solvatochromism. Thereby Stokes shifts in the range of 8950-10 440 cm 1 and quantum yields up to 0.70 were observed in dichloromethane solutions. In contrast to this, for the selenides 5 and 10 quantum yields are small (