Icosahedral metallacarboranes are q-shaped anionic molecules in which two icosahedra share one vertex that is am etal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C 2 B 9 H 11) 2 ] À , whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes[ Co(C 2 B 9 H 11) 2 ] À very appealingt o participatei ne lectron-transfer processes. In this work, [Co(C 2 B 9 H 11) 2 ] À is tethered to ap erylenediimided ye to produce the first examples of switchable luminescentm olecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C 2 B 9 H 11) 2 ] À with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systemsb ased on conjugates of perylendiimides with ferrocene. Remarkably,t hey can form gels by treatment with appropriate mixtureso fo rganic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimidec onjugates into 1D nanostructures. The interplay between dye p-stackinga nd metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangementi nt hese materials, which for one of the compoundsp repared allows preserving the luminescent behavior in the gel state.
Make it switch: By combining the versatile electrochemical behavior of cobalt‐based metallacarboranes with the excellent emission properties of perylenediimides, new fluorescent molecular switches were prepared that respond to redox stimuli. These systems not only surpass the performance of previous switches based on other metal complexes, but also allow the preparation of supramolecular fluorescent gels by taking advantage of the self‐assembly capabilities of their constituting units. More information can be found in the Full Paper by R. Núñez, J. Hernando, et al. on page 270.
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