Triphenylamine-substituted 2-pyridyl-1,2,3-triazole copper(I) complexes: an experimental and computational investigation

Four new heteroleptic copper(I) complexes bearing either 2-pyridyl-1,2,3-triazole (pytri) or the related triphenylamine (TPA) substituted (TPA-tripy) ligands and the ancillary ligands 6,6′-dimesityl-2,2′-bipyridine (diMesbpy) or bis[(2-diphenylphosphino)phenyl] ether (POP) were synthesized in good yields (75-95%). All the complexes were extensively characterized using nuclear magnetic resonance (NMR) spectroscopies and electrospray ionization mass spectrometry (ESIMS) and in the case of the two pytri compounds the solid state structures were determined via X-ray crystallography. The pytri complexes showed MLCT absorption bands which shift from 433 nm for the diMesbpy complex to 347 nm for POP. TPA-pytri complexes introduce an ILCT band resulting in improved visible absorption (376 nm, 26,400 M⁻¹ cm⁻¹ for [Cu(TPA-pytri)(diMesbpy)](PF₆)). Emission from this ILCT state (470 nm, Φ = 0.08) was red-shifted compared to the free ligand with negligible effects from ancillary ligands. Band assignments were confirmed with resonance Raman spectroscopy and TD-DFT calculations.