Solvent- and metal-gated coordination diversity in a dynamic aminal ligand

Area of Science:

• Coordination Chemistry
• Dynamic Covalent Chemistry
• Supramolecular Chemistry

Background:

• Dynamic covalent chemistry (DCC) offers versatile routes to complex molecular structures.
• Primary-amine-based aminals are under-explored ligands within DCC.
• Systematic investigation of aminal coordination chemistry is lacking.

Purpose of the Study:

• To investigate the coordination chemistry of primary-amine-based aminals.
• To demonstrate the adaptive scaffold potential of these aminals.
• To explore how solvent and metal ion influence outcomes in coordination complexes.

Main Methods:

• Synthesis of primary-amine-based aminal ligands.
• Coordination studies with various transition metal ions (Co, Cu, Fe).
• Structural characterization of resulting metal complexes using spectroscopy and X-ray diffraction.

Main Results:

• Cobalt(III) complexes showed stabilization of hemiaminalates in methanol and templated macrocyclization in acetonitrile.
• Copper(II) complexes yielded hemiaminal and hemiaminal ether structures.
• Iron(III) promoted pyridinium dimerization, forming unique cis-dimeric complexes.

Conclusions:

• Dynamic ligands can actively generate structural diversity in metal complexes.
• Aminal-based ligands serve as adaptive scaffolds for coordination chemistry.
• Findings open new avenues for designing functional coordination architectures.