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

The coordination-driven self-assembly methodology has emerged over the last few decades as an extraordinarily versatile synthetic tool for obtaining discrete macrocyclic or cage structures. Rational approaches using large libraries of ligands and metal complexes have allowed researchers to reach more sophisticated structures such interlocked, chiral, heteroleptic cages, some them are designed guest binding applications. Efforts been notably produced in controlling host-guest affinity with, particular, evident interest targeting substrate transportation subsequent delivering. Recent accomplishments this direction were described from functional cages which can be addressed with light, pH, through a chemical exchange. case redox-stimulation much less explored. In case, charge state redox-active cavity controlled applied electrical potential introduction appropriate oxidizing/reducing agent. Beyond possible applications electrochemical sensing environmental medical sciences well redox catalysis, offers possibility modulate electrostatic interactions, up point disassembly complex, i.e., releasing molecule host cavity.This Account highlights key studies that we carried out at Angers, related coordination-based architectures (i.e., metalla-rings, -cages, -tweezers). These species built upon metal-driven between electron-rich ligands, based on tetrathiafulvalene (TTF) moiety (as its S-rich derivatives), various complexes. Given high ?-donating character those corresponding exhibit electronic density panels. This situation is favorable bind complementary electron-poor guests, it was illustrated bis(pyrrolo)tetrathiafulvalene (BPTTF)-based cavities, hosting properties C60 tetrafluorotetracyanoquinodimethane (TCNQ-F4). addition pristine tetrathiafulvalene, successfully incorporated into palladium- ruthenium-based architectures, so-called extended (exTTF) appears particularly fascinating. A series polycationic neutral M4L2 ovoid containers, M6L3 cage, synthesized, their respective abilities anionic guests studied. Remarkably, allow control redox-stimulation, two distinctive processes: (i) disassembling (ii) displacement. As extension approach, metalla-assembled tweezers designed, able trigger release original process supramolecular dimerization activated stimulus. ensemble results illustrates remarkable ability electron-rich, self-assembled cavities types and, importantly, redox-stimulus.