Synthesis of panchromatic Ru(II) thienyl-dipyrrin complexes and evaluation of their light-harvesting capacity.

摘要: Ru(II) complexes with 5-(3-thienyl)-4,6-dipyrrin (3-TDP), containing 2,2′-bipyridine (bpy) or 4,4′-bis(methoxycarbonyl)-2,2′-bipyridine (dcmb) as coligands, have been prepared and extensively characterized. Crystal structure determination of [Ru(bpy)2(3-TDP)]PF6 (1a) [Ru(bpy)(3-TDP)2] (2) reveals that the 3-thienyl substituent is rotated respect to plane dipyrrinato moiety. These complexes, well [Ru(dcmb)2(3-TDP)]PF6 (1b), act panchromatic light absorbers in visible range, two strong absorption bands observable each case. A comparison known quantum-chemical calculations at density functional theory (DFT) level indicate lower-energy band due metal-to-ligand charge transfer (MLCT) excitation, although frontier occupied metal-based molecular orbitals (MOs) contain significant contributions from 3-TDP The higher energy assigned π–π* transition ligand. Each complex exhibits an easily ...