Electron-rich Coordination Receptors Based on Tetrathiafulvalene Derivatives: Controlling the Host–Guest Binding

Abstract

CONSPECTUS.The coordination-driven self-assembly methodology has emerged over the last decades as an extraordinary versatile synthetic tool for obtaining discrete macrocyclic or cage structures. Rational approaches using wide libraries of ligands and metal complexes have allowed to reach more and more sophisticated discrete structures such as interlocked, chiral or heteroleptic cages, and some of them are designed for guest binding applications. Efforts have been notably produced in controlling host-guest affinity with in particular, an evident interest for targeting substrate transportation and subsequent delivering. Recent accomplishments in this direction were described from functional cages which can be addressed with light, pH or through a chemical exchange. The case of a redox-stimulation has been much less explored. In this case, the charge state of the redox-active cavity can be controlled through an applied electrical potential or introduction of an appropriate oxidizing/reducing chemical agent. Beyond possible applications in electrochemical sensing for environmental and medical sciences as well as for redox catalysis, controlling the cavity charge offers the possibility to modulate the host-guest binding affinity KEY REFERENCES

Recent advances and perspectives on supramolecular radical cages

“…The construction of cages containing redox-active units, such as ferrocenyl, viologen dication, tetrathiafulvalene (TTF) and so on, is of great interest in supramolecular chemistry since such systems exhibit very intriguing redox properties. 15 In addition, redox-active cages in principle can electrochemically regulate the host–guest interaction with any charged or neutral guest. 16 Notably, one of the main issues and challenges of the synthesis of cages bearing polyradical cations or anions is the non-negligible electronic communication between each of the redox-active units that makes the oxidation or reduction of redox-active units, especially the adjacent redox-active units, more difficult.…”

Controlling Chiral Self-Sorting in Truxene-Based Self-Assembled Cages

“…The latter can be used to target applications such as molecular recognition, drug delivery, molecular separation or even catalysis in confined spaces [4][5][6][7][8][9][10][11][12][13][14]. In line with the work developed in the field of molecular machines, researchers are particularly interested in designing stimuli-responsive self-assembled structures, whose properties or shape can be tuned through light irradiation, application of a current or addition of a chemical [15][16][17][18][19][20][21][22][23]. Nevertheless, most of these self-assembled structures are achiral.…”

Gast‐modulierte Zirkular Polarisierte Lumineszenz via Ligand‐zu‐Ligand Chiralitätstransfer in Heteroleptischen PdII Käfigen

“…In den letzten Jahrzehnten haben Forscher zahlreiche artifizielle Wirtssysteme mit Funktionen wie selektiver Wirt-Gast-Interaktion, [6] Katalyse, [7][8][9] Sensorverhalten [10] und molekularem Transport [11][12][13] entwickelt. Die Wahl maßgeschneiderter Bausteine ermöglicht dabei die Einführung von funktionellen Einheiten wie Farbstoffen, [14,15] Photoschaltern, [16][17][18][19] Redoxzentren, [20][21][22][23][24] Luminophoren [25][26][27][28][29] oder chiralen Gruppen. [30][31][32][33][34][35][36][37] Dies kann zu neuartigen Eigenschaften führen, z.…”