Covalent non-fused tetrathiafulvalene–acceptor systems

Abstract

Covalent donor-acceptor (D-A) systems have significantly contributed to the development of many organic materials and to molecular electronics. Tetrathiafulvalene (TTF) represents one of the most widely studied donor precursors and has been incorporated into the structure of many D-A derivatives with the objective of obtaining redox control and modulation of the intramolecular charge transfer (ICT), in order to address switchable emissive systems and to take advantage of its propensity to form regular stacks in the solid state. In this review, we focus on the main families of non-fused TTF-acceptors, which are classified according to the nature of the acceptor: nitrogen-containing heterocycles, BODIPY, perylenes and electron poor unsaturated hydrocarbons, as well as radical acceptors. We describe herein the most representative members of each family with a brief mention of their synthesis and a special focus on their D-A characteristics. Special attention is given to ICT and its modulation, fluorescence quenching and switching, photoconductivity, bistability and spin distribution by discussing and comparing spectroscopic and electrochemical features, photophysical properties, solid-state properties and theoretical calculations.

Redox‐Guest‐Induced Multimode Photoluminescence Switch for Sequential Logic Gates in a Photoactive Coordination Cage

“…On the other hand, tetrathiafulvalene (TTF) is easily oxidized to the radical‐cation and dication species through two one‐electron processes sequentially and reversibly . This affords TTF as versatile building units in donor–acceptor systems to provide different chemophysical applications, including molecular switches, linear or nonlinear optics, electrical conductors, and so on . Therefore, TTF can be a good candidate in participating and tuning the electro‐ and photo‐properties of confined host–guest systems based on MOCs, although related studies remain scarce .…”

“…[14][15][16] On the other hand, tetrathiafulvalene (TTF) is easily oxidized to the radical-cation and dication species throught wo one-electron processes sequentially and reversibly. [17] This affords TTF as versatile building units in donor-acceptor systems to provide different chemophysical applications,i ncluding molecular switches, linear or nonlinear optics, electrical conductors, ands oo n. [18][19][20][21][22][23] Therefore, TTF can be ag ood candidate in participating and tuningt he electro-and photo-properties of confined hostguest systemsb ased on MOCs, althoughr elateds tudies remain scarce. [24,25] Especially,c onsidering the different oxidation states of TTF that are easily available by chemical, electrochemicalo rp hotochemical methods, an advanced PL responsive system with multi-step emission tuning abilities can be established by encapsulating TTF in hosts and then adjusting its oxidation states sequentially.I nt his way,m ultiple chemical and photonici nput/outputs ignals can be combined in the well-defined TTF&host systema tananosizeds upramolecular scale, providing feasible higher-levell ogic devices with com-plex and integrated functions.…”

Photo-physical properties of donor-acceptor-radical triad based on functionalized tetrathiafulvalene and nitronyl nitroxide radical

“…Whereas the first strategy leads to very weak π-d/π-f interactions, the second one might enhance them. The "through-space" approach is commonly used thanks to a plethora of functionalization of the TTF core with organic moieties suitable to coordinate metal ions (amino, nitrile, phenolate, phosphino, β-diketonate, pyrazine, pyrimidine, pyridine, pyridine-N-oxide, bipyridine…) [5], [21], [22]. All of these organic coordinating groups are magnetically innocent (S = 0).…”

Progress on Synthesis and Application of Triazole-Based Tetrathiafulvalene Derivatives

“…基于 TTF 三氮唑的[3]索烃 Switchable[3]rotacatenane with triazole-based TTF derivative声溶解, 利用 TTF 的供电子性质将氧化石墨烯(GO)还 原 来 构 筑 基 于 石 墨 烯 的 纳 米 杂 化 材 料 . 然 后 利 用 CuAAC 点击反应将其作为基质与含端基炔的甘露糖反 应得到含糖的石墨烯材料(Scheme 9).…”