Functionalised tetrathiafulvalene- (TTF-) macrocycles: recent trends in applied supramolecular chemistry

Abstract

Tetrathiafulvalene (TTF) has been extensively explored as a π-electron donor in supramolecular systems. Over the last two decades substantial advances have been made in terms of constructing elaborate architectures based on TTF and in exploiting the resulting systems in the context of supramolecular host-guest recognition. The inherent electron-donating character of TTF derivatives has led to their use in the construction of highly efficient optoelectronic materials, optical sensors, and electron-transfer ensembles. TTFs are also promising candidates for the development of the so-called "functional materials" that might see use in a range of modern technological applications. Novel synthetic strategies, coupled with the versatility inherent within the TTF moiety, are now allowing the architecture of TTF-based systems to be tuned precisely and modified for use in specific purposes. In this critical review, we provide a "state-of-the-art" overview of research involving TTF-based macrocyclic systems with a focus on their use in supramolecular host-guest recognition, as components in non-covalent electron transfer systems, and in the construction of "molecular machines".

Light emission enhancement by supramolecular complexation of chemiluminescence probes designed for bioimaging

“…The formation of a non-covalent inclusion complex between the TMCD host and alkaline phosphatase 1,2-dioxetane probe 1 in aqueous solution was validated by electrospray ionization mass spectrometry (ESI-MS) 56,57Fig.…”

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

“…In addition to MIMs switchable by light or chemical reagents, redox-switchable molecular assemblies are of particular interest, since redox switching at electrodes is considered to operate without chemical waste and electrochemical analytical tools, e.g., cyclic voltammetry (CV), exhibit great potential to investigate the kinetic and thermodynamic parameters of the switching processes [ 32 – 33 ]. Although various redox-active crown ethers have been described [ 14 , 21 , 34 ], they are not commonly implemented into crown ether/ammonium (pseudo)rotaxanes. One reason is that functionalized crown ethers can cause major obstacles in the synthesis of (pseudo)rotaxanes, as their functionalization can strongly interfere with the binding properties of the crown ether [ 24 – 25 ].…”

“…Redox-switchable crown ethers have been shown to sense cations by the generation of an electrochemical output. For example, crown ethers containing tetrathiafulvalene (TTF) derivatives, which enable two reversible oxidation processes from the neutral to the dicationic state, were applied to sense various cations, e.g., alkali metal ions, Pb 2+ , and Ba 2+ [18][19][20][21].…”

Charge-transfer interactions between fullerenes and a mesoporous tetrathiafulvalene-based metal–organic framework

“…Tetrathiafulvalene (TTF) and its numerous derivatives are redox-active electron-donor molecules with unique electronic properties that have been widely used as important building units in the field of molecular electronics as conductors, switches, sensors or rectifiers [37–38]. Several studies have also been devoted to the development of TTF-based macrocyclic systems for their use as molecular machines or for supramolecular host–guest recognition [39–41]. In this context, donor–acceptor interactions between C 60 and discrete π-extended TTF molecules have been extensively studied in solution during the last years [42–47].…”