Peripherally substituted tetradecaazaheptacene (N(14)Hp) compounds, exhibiting amphiprotism-coupled emission, have been synthesized. X-ray crystallography reveals a planar acene-like chromophore, and electronic absorption and emission occur in the near-infrared biological transparency window (650-900 nm). The compounds exhibit long-wavelength emission with photoluminescence quantum yields Phi(PL) up to similar to 0.61 at 686 nm, with the monodeprotonated state Phi(PL) approximate to 0.58 at 712 nm. This unprecedented highly nitrogenous chromophore illustrates the stability and utility of the pyrazinacenes for different applications based on their photophysical properties and chemical structures.