Bichromophoric Photosensitizers: How and Where to Attach Pyrene Moieties to Phenanthroline to Generate Copper(I) Complexes

Abstract

Pyrene is a polycyclic aromatic hydrocarbon and organic dye that can form superior bichromophoric systems when combined with a transition metal-based chromophore. However, little is known about the effect of the type of attachment (i.e., 1- vs 2-pyrenyl) and the individual position of the pyrenyl substituents at the ligand. Therefore, a systematic series of three novel diimine ligands and their respective heteroleptic diimine-diphosphine copper(I) complexes has been designed and extensively studied. Special attention was given to two different substitution strategies: (i) attaching pyrene via its 1-position, which occurs most frequently in the literature, or via its 2-position and (ii) targeting two contrasting substitution patterns at the 1,10-phenanthroline ligand, i.e., the 5,6- and the 4,7-position. In the applied spectroscopic, electrochemical, and theoretical methods (UV/vis, emission, time-resolved luminescence and transient absorption, cyclic voltammetry, density functional theory), it has been shown that the precise choice of the derivatization sites is crucial. Substituting the pyridine rings of phenanthroline in the 4,7-position with the 1-pyrenyl moiety has the strongest impact on the bichromophore. This approach results in the most anodically shifted reduction potential and a drastic increase in the excited state lifetime by more than two orders of magnitude. In addition, it enables the highest singlet oxygen quantum yield of 96% and the most beneficial activity in the photocatalytic oxidation of 1,5-dihydroxy-naphthalene.