Designing molecules that can undergo late-stage modifications resulting in specific optical properties is useful for developing structure-function trends in materials, which ultimately advance optoelectronic applications. Herein, we report a series of fused diborepinium ions stabilized by carbene and carbone ligands (diamino-N-heterocyclic carbenes, cyclic(alkyl)(amino) carbenes, carbodicarbenes, and carbodiphosphoranes), including a detailed bonding analysis. These are the first structurally confirmed examples of diborepin dications and we detail how distortions in the core of the pentacyclic fused system impact aromaticity, stability, and their light-emitting properties. Using the same fused diborepin scaffold, coordinating ligands were used to dramatically shift the emission profile, which exhibit colors ranging from blue to red (350-650 nm). Notably, these diborepinium ions access expanded regions of the visible spectrum compared to known examples of borepins, with quantum yields up to 60%. Carbones were determined to be superior stabilizing ligands, resulting in improved stability in the solution- and solid-states. Density functional theory was used to provide insight into the bonding as well as the specific transitions that result in the observed photophysical properties.