Tetrathiafulvalene (TTF) as the prototypical electron donor for solid-state (electronics) applications is converted to the unusual cation-radical salt, TTF+center dot CB- (where CB- is the non-coordinating closo-dodecamethylcarboranate), for crystallographic and spectral analyses. Near-IR studies establish the spontaneous self-association of TTF+center dot to form the diamagnetic [TTF+,TTF+] dication and to also undergo the equally rapid cross-association with its parent donor to form the mixed-valence [TTF+center dot,TTF] cation-radical. The latter, most importantly, represents the first (dyad) member of a series of p-doped tetrathiafulvalene (stacked) arrays, and the thorough scrutiny of its electronic structure with the aid of Mulliken-Hush (two-state) analysis of the diagnostic (intervalence) NIR band reveals Robin-Day Class II behavior. The theoretical consequences of the unique structure of the mixed-valence [TTF+center dot,TTF] dyad on (a) the electron-transfer mechanism for self-exchange, (b) the molecular-orbital analysis of the Marcus reorganization energy, and (c) the ab initio computation of the coupling element or transfer integral in p-doped (solid-state) arrays are discussed.