Year: 2025
Type: article
Abstract: Due to the reversible nature of the metal–ligand bond, coordination cages are inherently dynamic architectures which can undergo structural transformations upon appropriate external stimulations. This adaptability has been widely explored in various fields. Herein, we report the preparation of a redox‐responsive discrete (Ru 2 ) 4 L 2 architecture through a coordination‐driven self‐assembly approach, where Ru 2 is a bis(ruthenium(II)) complex and L a tetrapyridyl ligand. Importantly, ligand L is designed around the π‐extended tetrathiafulvalene framework (exTTF), whose geometry is highly sensitive to its redox state. The resulting (Ru 2 ) 4 L 2 assembly was fully characterized, revealing a twisted configuration with two orthogonally oriented L units in close spatial proximity. Remarkably, this assembly undergoes an oxidation‐induced transformation into a (Ru 2 ) 4 L ox ₂ structure, in which the two dicationic ligands are now spatially separated and aligned according to a face‐to‐face arrangement, affording a cage‐like structure. This reorganization is driven by the redox‐induced geometric and electronic changes of the exTTF cores and the resulting electrostatic repulsions occurring between both oxidized ligands. The process is fully reversible upon chemical reduction, restoring the original (Ru 2 ) 4 L₂ structure.
Source: Chemistry - A European Journal
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
OpenAlex ID: W4411112253