Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway.
An electroactive M2L2 metalla-macrocycle constructed through coordination driven self-assembly dimerizes upon oxidation and binds an electro-deficient substrate with a high association constant.
Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway.
The development of methodologies to control on demand and reversibly supramolecular transformations from self-assembled metalla-structures requires the rational design of architectures able to answer to an applied stimulus. While solvent or concentration changes, light exposure or addition of a chemical have been largely explored to provide these transformations, the case of pH sensitive materials is less described. Herein, we report the first example of a pH-triggered dissociation of a coordination-driven self-assembled interlocked molecular link. It incorporates a pH sensitive benzobisimidazole-based ligand that can be selectively protonated on its bisimidazole moieties. This generates intermolecular electrostatic repulsions that reduces drastically the stability of the interlocked structure, leading to its dissociation without any sign of protonation of the pyridine moieties involved in the coordination bonds. Importantly, the dissociation process is reversible through addition of a base.
The synthesis of a new tetratopic extended-TTF (exTTF; 9,10-di(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene) ligand, bearing the four pyridyl coordinating functions on the dihydroanthracenyl platform rather than on the 1,3-dithiol rings (previously described regioisomer), is...
Pillar[5]arene derivatives decorated with ten peripheral TTF subunits have been efficiently prepared from a decabrominated pillar[5]arene building block and appropriate TTF-thiolate nucleophiles. While the preparation of related systems with peripheral...
M4L2 Metalla-cages bearing large electron-rich ovoid cavities constructed through coordination-driven self-assembly from square planar palladium complexes and extended tetrathiafulvalene (exTTF)-based ligands are depicted. Their binding properties for polyaromatic hydrocarbons (PAHs)...
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