Simple thermodynamics for unravelling sophisticated self-assembly processes

Area of Science:

• Coordination Chemistry
• Supramolecular Chemistry
• Chemical Thermodynamics

Background:

• Coordination chemistry has advanced towards multicomponent assemblies using multiple ligands and metal ions.
• Structural aspects of complexation reactions are well-recognized for designing molecular architectures.
• Energetic aspects of self-assembly are emerging as key for controlling and programming these processes.

Purpose of the Study:

• To focus on modeling free energy changes during self-assembly processes in coordination chemistry.
• To adapt the protein-ligand model for describing multicomponent assemblies.
• To analyze cooperativity and entropic contributions in complexation reactions.

Main Methods:

• Adaptation of the protein-ligand model to coordination chemistry.
• Introduction of concepts for cooperativity (extra energy cost from intercomponent interactions).
• Incorporation of entropic concepts separating intra- and intermolecular complexation.
• Development of the extended site binding model.

Main Results:

• The adapted protein-ligand model addresses cooperativity in multicomponent assemblies.
• Separating intra- and intermolecular complexation provides insights into entropic contributions.
• The extended site binding model dissects free energy changes using minimal microscopic parameters.
• Applications demonstrate the potential and limitations of the discussed models.

Conclusions:

• Thermodynamic modeling is crucial for understanding and controlling complex self-assembly processes.
• The extended site binding model offers a powerful tool for analyzing sophisticated metal-ligand systems.
• This work provides a framework for dissecting energetic contributions in multicomponent coordination chemistry.