Energy Migration Processes in Re(I) MLCT Complexes Featuring a Chromophoric Ancillary Ligand

We present the synthesis, structural characterization, [electronic structure calculations, and ultrafast and supra-nanosecond photophysical properties of a series of five Re(I) bichromophores exhibiting metal to ligand charge transfer (MLCT) excited states based on the general formula fac-[Re((NN)-N-boolean AND)(CO)(3) (PNI-py)]PF6, where PNI-py is 4-piperidinyl-1,8-naphthalimidepyridine and (NN)-N-boolean AND is a diimine ligand (Re1-5), along with their corresponding model chromophores where 4-ethylpyridine was substituted for PNI-py (Mod1-5). The diimine ligands used include 1,10-phenanthroline (phen, 1), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bcp, 2), 4,4'-di-tent-butyl-2,2'-bipyridine (dtbb, 3), 4,4'-diethyl ester-2,2'- bipyridine (deeb, 4), and 2,2'-biquinoline (biq, 5). In these metal-organic bichromophores, structural modification of the diimine ligand resulted in substantial changes to the observed energy transfer efficiencies between the two chromophores as a result of the variation in (MLCT)-M-3 excited-state energies. The photophysical properties and energetic pathways of the model chromophores were investigated in parallel to accurately track the changes that arose from introduction of the organic chromophore pendant on the ancillary ligand. All relevant photophysical and energy transfer processes were probed and characterized using time-resolved photoluminescence spectroscopy, ultrafast and nanosecond transient absorption spectroscopy, and time-dependent density functional theory calculations. Of the five bichromophores in this study, four (Re1-4) exhibited a thermal equilibrium between the (PNI)-P-3-py and the (MLCT)-M-3 excited state, drastically extending the lifetimes of the parent model chromophores.