CE06 - Polymères, composites, physique et chimie de la matière molle, procédés

Polycatenation of Donor-Acceptor Coordination Cages – PoDACC

Submission summary

The coordination-driven self-assembly strategy is remarkably efficient in building discrete polygons and cages, unreachable through usual covalent chemistry. This approach, directed through thermodynamic control, is supported by both the highly predictable directionality of the metal-ligand coordination sphere and the reversible nature of the coordination bonds. In addition to discrete structures, topologically more complex assemblies have appeared in the recent literature, and correspond to interlocked cages (based on interpenetrated systems). A step further was also realized through the formation of their respective oligomeric/polymeric analogues, i.e. polycatenated cages. At this stage, it appears that there is an urgent need to address the scope of this new fascinating family of compounds, both in terms of rational design guiding their synthesis and by exploring their unique characteristics towards new applied scientific frontiers.
The proposed PoDACC project aspires to address these issues, through designing a select family of hybrid cages, featuring both electron-donor (D) and -acceptor (A) units. Detailed investigations of such original self-assembled structures will: 1) address the basics for the formation of interlocked coordination cages, and will extend the concept to polycatenated cages; 2) enable an original redox-assisted synthesis of interlocked architectures, through enhanced intermolecular interactions, a key factor to overcome the entropy cost related to the construction of such objects; 3) control the relative organization and stoichiometry of D and A partners in the supramolecular system, leveraging the unique topology of the target interlocked architectures. The synthetic parameters and the resulting structures and photophysical properties of the supramolecular assemblies will be assessed through coupled theoretical and experimental approaches, the latter involving solid-state NMR, spectroelectrochemical measurements, electrocrystallization, FT-ICR mass spectrometry and DFT. Finally, such innovative self-assembled materials will provide unique opportunities to assess this new family of structurally controlled architectures for molecular electronics applications.

Project coordination

Sébastien Goeb (MOLTECH-Anjou)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.


NC State University / Department of Chemistry, Felix N. Castellano
CRMN Centre de RMN à Très Hauts Champs de Lyon

Help of the ANR 422,217 euros
Beginning and duration of the scientific project: - 48 Months

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