Simultaneous Generation of a [2 × 2] Grid-Like Complex and a Linear Double Helicate: a Three-Level Self-Sorting...

Area of Science:

• Supramolecular Chemistry
• Coordination Chemistry
• Materials Science

Background:

• Constitutional dynamic libraries (CDLs) are mixtures of components that can rearrange to form new structures.
• Self-sorting is a process where components in a mixture selectively combine to form specific architectures.
• Imine-based metallosupramolecular architectures offer tunable properties through metal coordination and ligand design.

Purpose of the Study:

• To investigate the self-sorting behavior of CDLs containing amines, dialdehydes, and metal salts.
• To demonstrate a three-level self-sorting process in the formation of imine-based metallosupramolecular architectures.
• To synthesize and characterize novel [2 × 2] grid-like complexes and linear double helicates.

Main Methods:

• Assembly of two distinct constitutional dynamic libraries, each with two amines, two dialdehydes, and two metal salts.
• Characterization of the self-sorted metallosupramolecular architectures using Nuclear Magnetic Resonance (NMR) spectroscopy.
• Analysis of the assembled structures via mass spectrometry and X-ray crystallography.

Main Results:

• Two CDLs successfully self-sorted, yielding two distinct pairs of imine-based metallosupramolecular architectures.
• Each pair consisted of a [2 × 2] grid-like complex and a linear double helicate, with no shared components between pairs.
• A three-level self-sorting process was observed, selecting only two specific ligand constituents, two metal complexes, and two final architectures.

Conclusions:

• Constitutional dynamic libraries provide a powerful platform for the controlled assembly of complex metallosupramolecular architectures.
• The observed three-level self-sorting demonstrates high selectivity in the formation of discrete supramolecular structures.
• This work expands the toolkit for designing and synthesizing novel imine-based metallosupramolecular systems with potential applications in materials science.