Rhenium(I) polypyridyl complexes have been designed for the intramolecular photogeneration of tyrosyl radical. Tyrosine (Y) and phenylalanine (F) have each been separately appended to a conventional Re-1(bpy)(CO)(3)CN framework via an amide linkage to the bipyridine (bpy) ligand. Comparative time-resolved emission quenching and transient absorption spectra of Re(bpy-Y)(CO)(3)CN and Re(bpy-F)(CO)(3)CN show that Y is oxidized only upon its deprotonation at pH 12. In an effort to redirect electron transport so that it is more compatible with intramolecular Y oxidation, polypyridyl Re-1 complexes have been prepared with the amide bond functionality located on a pendant phosphine ligand. A [Re(phen)(PP-Bn)(CO)(2)](PF6) (PP = bis(diphenylphosphino)ethylene) complex has been synthesized and crystallographically characterized. Electrochemistry and phosphorescence measurements of this complex indicate a modest excited-state potential for tyrosine oxidation, similar to that for the (bpy)Re-1(CO)(3)CN framework. The excited-state oxidation potential can be increased by introducing a monodentate phosphine to the Re-1(NN)(CO)(3)(+) framework (NN = polypyridyl). In this case, Y is oxidized at all pHs when appended to the triphenylphosphine (P) of [Re(phen)(P-Y)(CO3)](PF6). Analysis of the pH dependence of the rate constant for tyrosyl radical generation is consistent with a proton-coupled electron transfer (PCET) quenching mechanism.