Linear and star-shaped polynuclear Ru(ii) complexes of 2-(2′-pyridyl)benzimidazolyl derivatives: syntheses, photophysical properties and red light-emitting devices

Abstract

Two new star-shaped ligands with a 1,3,5-triphenylbenzene core, tmpb (1,3,5-tris[p-2-(2′-pyridyl)benzimidazolylphenyl]benzene), and a 2,4,6-tris(p-biphenyl)-1,3,5-triazine core, tmbt (2,4,6-tris[p-2-(2′-pyridyl)benzimidazolylbiphenyl]-1,3,5-triazine), have been synthesized. Their corresponding trinuclear Ru(II) complexes [Ru₃(tmpb)(bpy)₆](PF₆)₆ (3) and [Ru₃(tmpt)(bpy)₆](PF₆)₆ (4) have been obtained. Two dinuclear linear Ru(II) complexes with previously reported ligands bmb (1,4-bis[2-(2′-pyridyl)benzimidazolyl]benzene) and bmbp (4,4′-bis[2-(2′-pyridyl)benzimidazolyl]biphenyl) and formulae [Ru₂(bmb)(bpy)₄](PF₆)₄ (1) and [Ru₂(bmbp)(bpy)₄](PF₆)₄ (2) have also been synthesized. Photophysical and electrochemical properties of the new compounds have been investigated. All four compounds display a characteristic metal-to-ligand-charge transfer (MLCT) absorption band and emit a red light when excited at the maximum of the MLCT band with emission maximum at 624, 629, 623 and 625 nm, respectively in neat films at ambient temperature. The emission quantum efficiency of the four complexes in neat films was determined to be 0.15, 0.17, 0.04 and 0.05, respectively. Light emitting devices based on these four compounds were fabricated by spin-casting the compound as a neat film to an ITO substrate, followed by the deposition of an aluminium metal layer. All devices emit a deep red light and the device behavior resembles that of a light emitting electrochemical cell. The EL maximum of the devices 1, 2, 3, and 4 is at 637, 657, 678, and 655 nm, respectively. All four devices have a fast response time when a sufficiently high voltage is applied. The device based on 2 is the brightest with a maximum luminance of 133 cd m⁻² at 7 V. The performance of devices based on 1, 2, and 4 is in general much more efficient than the device based on [Ru(bpy)₃](PF₆)₂, which was fabricated and evaluated under the same experimental conditions as for the devices based on 1–4.