Boron complexes of aromatic 5-substituted iminopyrrolyl ligands: synthesis, structure, and luminescence properties

Abstract

A group of new mononuclear boron chelate compounds [BPh₂{κ²N,N′-5-R-NC₄H₂-2-C(H)N–Ar}] (R = Ar = C₆H₅7; R = C₆H₅, Ar = 2,6-iPr₂C₆H₃8; R = Anthracen-9-yl (Anthr), Ar = C₆H₅9; R = Anthr, Ar = 2,6-iPr₂C₆H₃10) were synthesized via the reaction of B(C₆H₅)₃ with the corresponding 5-substituted 2-(N-arylformimino)pyrrole ligand precursors 3–6. These complexes were prepared in order to evaluate the luminescence potential derived from the substitution of the position 5 of the pyrrolyl ring with an aromatic group. Compounds 7–10 were photophysically characterized in solution and in the solid state. The 5-phenyl-2-iminopyrrolyl-BPh₂ complexes 7 and 8 are blue emitters and have enhanced photoluminescence quantum yields in the solid state (Φ_PL) up to 0.95, whereas the 5-anthracenyl derivatives 9 and 10 have green-bluish fluorescence and a Φ_PL of 0.49 and 0.24, respectively. DFT and TDDFT studies were performed, considering the effect of solvent and dispersion, in order to show how the geometries of compounds 7–10 changed from the ground to the excited state, to assign electronic transitions, and to rationalize the observed luminescence. These materials were applied in organic light-emitting diodes (OLEDs), with various device structures, the best showing an external quantum efficiency of 2.75% together with a high luminance of 23 530 cd m⁻².