Reactions between the pi-acidic cyclic trimetallic coinage metal(I) complexes {[Cu(mu-3,5-(CF3)(2)pz)](3), {[Ag(mu-3,5-(CF3)(2)pz)](3), and {[Au(mu-3,5-(CF3)(2)pz)](3) with TTF, DBTTF and BEDT-TTF give rise to a series of coinage metal(I)-based new binary donor-acceptor adducts {[Cu(mu-3,5-(CF3)(2)pz)](3)DBTTF} (1), {[Ag(mu-3,5-(CF3)(2)pz)](3)DBTTF} (2), {[Au(mu-3,5-(CF3)(2)pz)](3)DBTTF} (3), {[Cu(mu-3,5-(CF3)(2)pz)](3)TTF} (4), {[Ag(mu-3,5-(CF3)(2)pz)](3)TTF} (5), {[Au(mu-3,5-(CF3)(2)pz)](3)TTF} (6), {[Cu(mu-3,5-(CF3)(2)pz)](3)BEDT-TTF} (7), {[Ag(mu-3,5-(CF3)(2)pz)](3)BEDT-TTF} (8), and {[Au(mu-3,5-(CF3)(2)pz)](3)BEDT-TTF} (9), where pz = pyrazolate, TTF = tetrathiafulvalene, DBTTF = dibenzotetrathiafulvalene, and BEDT-TTF = bis-(ethylenedithio)tetrathiafulvalene. This series of binary donor-acceptor adducts has been found to exhibit remarkable supramolecular structures in both the solid state and solution, whereby they exhibit supramolecular stacked chains and oligomers, respectively. The supramolecular solid-state and solution binary donor-acceptor adducts also exhibit superior shelf stability under ambient laboratory storage conditions. Structural and other electronic properties of solids and solutions of these adducts have been characterized by single-crystal X-ray diffraction (XRD) structural analysis, 1H and 19F NMR, UV-vis-near-IR spectroscopy, Fourier transform infrared, and computational investigations. The combined results of XRD structural data analysis, spectroscopic measurements, and theoretical studies suggest sustenance of the donor-acceptor stacked structure and electronic communication in both the solid state and solution. These properties are discussed in terms of potential applications for this new class of supramolecular binary donor-acceptor adducts in molecular electronic devices, including solar cells, magnetic switching devices, and field-effect transistors.