Trigonal NHC bis-pyridyl silver(i) complexes: a beacon of light in the darkness of light-emitting electrochemical cells?

Complex [Ag(IPr)(^3-Medpa)][PF₆] (1), possessing the same combination of ligands as previously reported [Cu(IPr)(^3-Medpa)][PF₆] (2) applied in a blue-emitting light-emitting electrochemical cell (LEC), has been synthesized and fully structurally and photophysically characterized both in powder and thin-film form. In detail, temperature-dependent steady-state, time-resolved emission experiments, and computational calculations have been performed to understand the impact of the nature of the metal ion center on the photophysical and electroluminescent properties. Here, a direct comparison between the complexes reveals (i) a distinct emission behavior, such as fluorescence (1) vs. thermally activated delay fluorescence (2), caused by the changes of the nature of the emitting excited states from ligand centered (1) to metal-to-ligand charge transfer (2), (ii) an unforeseen crystallinity-dependent emission in 1 that leads to either smooth and non-emissive thin-films or phase aggregated and emissive thin-films, and (iii) 1-based LECs with a stable electrical behavior over 100 h, which contrasts with the prior start-of-the-art value of a few minutes (2).