Binary Donor–Acceptor Adducts of Tetrathiafulvalene Donors with Cyclic Trimetallic Monovalent Coinage Metal Acceptors

Abstract

Reactions between the π-acidic cyclic trimetallic coinage metal(I) complexes {[Cu(μ-3,5-(CF₃)₂pz)]₃, {[Ag(μ-3,5-(CF₃)₂pz)]₃, and {[Au(μ-3,5-(CF₃)₂pz)]₃ with TTF, DBTTF and BEDT-TTF give rise to a series of coinage metal(I)-based new binary donor-acceptor adducts {[Cu(μ-3,5-(CF₃)₂pz)]₃DBTTF} (<b>1</b>), {[Ag(μ-3,5-(CF₃)₂pz)]₃DBTTF} (<b>2</b>), {[Au(μ-3,5-(CF₃)₂pz)]₃DBTTF} (<b>3</b>), {[Cu(μ-3,5-(CF₃)₂pz)]₃TTF} (<b>4</b>), {[Ag(μ-3,5-(CF₃)₂pz)]₃TTF} (<b>5</b>), {[Au(μ-3,5-(CF₃)₂pz)]₃TTF} (<b>6</b>), {[Cu(μ-3,5-(CF₃)₂pz)]₃BEDT-TTF} (<b>7</b>), {[Ag(μ-3,5-(CF₃)₂pz)]₃BEDT-TTF} (<b>8</b>), and {[Au(μ-3,5-(CF₃)₂pz)]₃BEDT-TTF} (<b>9</b>), 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.