The copper quinone interaction plays important roles in diverse fields such as biochemistry, catalysis, and optically/magnetically switchable materials. Despite this fact, the isolation and thorough characterization of copper(I)quinone complexes remains a highly challenging task owing to their intrinsic instability. We herein present systems where the stability imparted by the extended 7r-system of a pyrene ring is used to synthesize, isolate, and crystallographically characterize the first example of a dinuclear metal complex that is bridged by a completely unreduced "di-o-quinone"-type ligand. Additionally, we present the monocopper counterpart with the o-quinone pyrene type of ligand. The copper complexes are redox-rich and display intriguing electrochemical, optical, and electron paramagnetic resonance (EPR) spectroscopic properties. The line-rich EPR spectra of the one-electron reduced copper(I) complexes were simulated and analyzed via density functional theory calculations. The results presented here establish 7r ir stacking as a viable alternative to stabilize otherwise unstable redox-active compounds with possible consequences for sensing and redox catalysis.