Synthesis, structure and density functional theory calculations of a novel photoluminescent trisarylborane-bismuth(III) complex.

Abstract

A novel trisarylborane-Bi(III) complex, tris(4-(dimesitylboryl)phenyl)bismuthine [Bi(PhBMes2 )3 ], in which (Ph=phenyl, and Mes=mesityl), was synthesized via the reaction of bismuth (III) chloride (BiCl3 ) with three equivalents of lithiated (4-bromophenyl)- dimesitylborane [BrPhBMes2 ]. The new trisarylbismuthine was characterized by elemental analysis, ultraviolet-visible (UV-vis) spectroscopy, and NMR (1 H and 13 C) spectroscopy. The molecular structure of Bi(PhBMes2 )3 in the solid state was determined using single-crystal X-ray diffraction analysis, which showed short intermolecular C-H···H-C contact. The complex is a fluorescent emitter (λmax =395nm) at room temperature and a phosphorescent emitter (λmax =423nm) at 77K, which displayed a long lifetime of 495ms. The UV-vis transitions were investigated using density function theory (DFT) and time-dependent (TD)-DFT calculations. Natural bond orbital analysis showed that the bismuth (III) center was mainly Lewis acidic in nature.