Controlling the guest expulsion process from ar eceptor is of critical importance in various fields.S everal coordination cages have been recently designed for this purpose,b ased on various types of stimuli to induce the guest release.Herein, we report the first example of aredox-triggered process from acoordination cage.The latter integrates acavity, the panels of which are based on the extended tetrathiafulvalene unit (exTTF). The unique combination of electronic and conformational features of this framework (i.e.h igh pdonating properties and drastic conformational changes upon oxidation) allows the reversible disassembly/reassembly of the redox-active cavity upon chemicaloxidation/reduction, respectively.This cage is able to bind the three-dimensional B 12 F 12 2À anion in a1 :2 host/guest stoichiometry.T he reversible redoxtriggered disassembly of the cage could also be demonstrated in the case of the host-guest complex, offering an ew option for guest-delivering control.The control of the binding/release process of ag uest substance by ah ost molecule is of potential interest for awide range of applications,including drug delivery,catalysis, sensing or capture of hazardous agents/pollutants.F or this purpose,s ystems capable of tuning the host-guest binding affinity are required. On the other hand, the coordinationdriven strategy has been successfully used for the building of am yriad of host molecules [1] and important efforts are currently devoted to the construction of metallacages which are able to bind/release aguest on demand. [2] Afirst possible approach focuses on addressable guests,t he chemical modification of which (e.g. upon protonation, oxidation or irradiation) [3] leads to their release from the host. Alternatively,s timuli-responsive metallacages are gaining more and more interest. An evident interest of this approach lies in the independence on the guest structure and the fact that the latter keeps its chemical integrity along the binding/release process.Inthis approach, the guest release can be obtained by ac hange of the host cavity shape/size through as tructural rearrangement of the metallacage or even by its disassembly. Outstanding results were recently described by using various stimuli, such as light [4] or addition of ac hemical (e.g. protonation or component displacement), [3a, 5] some of these processes being reversible.N evertheless,t ot he best of our knowledge,there is still no example depicting aguest release which is redox-triggered from ac oordination-driven selfassembled cage,d espite this approach has been established with covalent macrocyclic hosts. [6] Additional benefits are awaited from metal-driven self-assembled receptors,since the latter involve labile metal-ligand bonds which in principle, can allow ar eversible disassembly by using an appropriate stimulus.T his was indeed observed by introducing acompetitive chemical to the coordination cage,t hat is,a ddition of an ew ligand or am etal, respectively. [4a,d, 5d,e,g,i] On this basis, ac age disassembling proce...