Semiconducting π‐Extended Tetrathiafulvalene Derivatives

Abstract

Tetrathiafulvalene (TTF) has been one of the most studied compounds, since the discovery of electrical conductivity as a charge-transfer complex in combination with tetracyano-p-quinodimethane (TCNQ) in 1973. In 2004, TTF was realized in a new light as an innate semiconductor material, as well as conductor and superconductor material. Because of the ready modification of its core skeleton and better solubility than that of acene compounds, many TTF derivatives have been reported to attain better charge-carrier mobility for field-effect transistor devices. Considering the high charge-carrier mobility of acene and TTF derivatives, annulation of the acene and TTF moieties is expected to improve the charge-carrier mobilities. This Minireview focuses on the syntheses, crystal structures, and electronic properties of state-of-the-art π-extended TTF derivatives, based on the history of the development of TTF derivatives. The relationship between the packing structure and charge-carrier mobilities is also discussed.

A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms

“…Moreover, their extended, planar π system offers a structural template well-poised for π stacking, while the sulfur atoms may engage in intermolecular S···X and S···S interactions. All of these assets have made TTFs favorite donor constituents of CT compounds when combined with a strong electron acceptor. ,− …”

Melamine sponge skeleton loaded organic conductors for mechanical sensors with high sensitivity and high resolution

“…In 1954, Akamatsu et al discovered the conductive charge transfer complex salts of perylene bromide complexes [39] . Since then, a variety of organic conductive materials have been developed, including a variety of small molecules, charge transfer complexes, oligomers and conductive polymers [40] . Their conductive mechanism is mainly due to the interaction between adjacent molecules and the intrinsic electronic structure of the extended molecule.…”

“…The main skeleton of TTF contains S atoms, which contribute to solid intermolecular S•••S interactions. These S•••S interactions and π-π and •CH-π interactions affect the stacking structure of TTF molecules in the crystal and further affect the electrical conductivity of the material [40] . The high conductivity of TTF-TCNQ CTC is attributed to a"herring bone"-type crystal structure formed by the at TTF and TCNQ, in which orbitals on adjacent molecules overlap to form continuous one-dimensional bands [42] .…”

Electrocatalytic Behavior of Tetrathiafulvalene (TTF) and Extended Tetrathiafulvalene (exTTF) [FeFe] Hydrogenase Mimics

“…Tetrathiafulvalene (TTF) derivatives have been thoroughly studied in molecular and noncovalent chemistry because of their unique π-electron-donating properties. , The incorporation of TTF and extended tetrathiafulvalenes (exTTFs) as the donor moiety in donor–acceptor (D–A) systems is currently a well-established methodology in the building of organic-based materials with applications in different fields related to organic electronic devices . In this regard, the oxidation of TTFs and exTTFs has been thoroughly and extensively studied because of their fundamental role in D–A organic molecules and devices. ,,− The electrochemical oxidation of the neutral TTF shows two reversible and well-separated one-electron steps, which account for the formation of the radical cation and dicationic species, respectively. − These processes result in the intramolecular charge transfer (ICT) associated with the ground state of oxidized TTF derivatives …”

“…The combination of TTF and exTTFs with [FeFe] hydrogenase models is appealing, not only for their redox properties but also for their unique self-assembly properties and their ability to interact with planar polyaromatic hydrocarbons (PAHs) through π–π interactions. These properties render them ideal candidates for the design of supramolecular models of [FeFe] hydrogenases able to interact with aromatic substrates or, by extension, with graphite or modified graphite surfaces. − ,− …”