Perylene Diimide-Derived Bis(Macrocyclic) Ligand Affords Chiral Multinuclear Pd(II) Complexes via Direct Bay-Region...

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Organic Electronics

Background:

• Macrocyclic ligands are crucial for constructing multi-metallic architectures.
• Direct π-core metalation of imide-functionalized polycyclic aromatic dyes is challenging.
• Controlling metalation in perylene diimide (PDI) systems is key for advanced materials.

Purpose of the Study:

• To design and synthesize a novel nitrogen-rich bis(macrocyclic) ligand based on a PDI scaffold.
• To achieve controlled direct C─H palladation at the PDI π-core.
• To explore the electronic and optical properties of the resulting multinuclear palladium complexes.

Main Methods:

• Synthesis of a new perylene diimide-based bis(macrocyclic) ligand.
• Palladium(II) coordination and subsequent direct C─H palladation.
• Characterization using ultrafast transient absorption and OTTLE spectroelectrochemistry.

Main Results:

• Successful synthesis of bis-Pd and tetra-Pd complexes (1-Pd2 and 1-Pd4) via direct palladation.
• Induction of conformational chirality in the macrocyclic framework due to palladation.
• Observation of altered excited-state dynamics and enhanced near-infrared absorption in reduced complexes.

Conclusions:

• Established a feasible synthetic route for direct metalation of PDI dyes.
• Demonstrated strong dye-metal electronic coupling in the multinuclear complexes.
• Highlighted the potential of these chiral multinuclear complexes as tunable multi-metallic π-systems.