Solvent-Induced Pathway Complexity of Supramolecular Polymerization Unveiled Using the Hansen Solubility Parameters

Area of Science:

• Supramolecular Chemistry
• Polymer Science
• Materials Science

Background:

• Supramolecular polymerizations form helical aggregates, but solvent roles are often unclear.
• Understanding solvent-supramolecular interactions is key to controlling self-assembly.

Purpose of the Study:

• To systematically quantify solvent-supramolecular polymer compatibility.
• To develop a predictive model for supramolecular polymerization pathways.
• To explore solvent-induced complexity in self-assembly.

Main Methods:

• Utilized Hansen solubility parameters (δD, δH, δP) to map solubility.
• Employed a dual-sphere model for monomeric and polymeric states.
• Investigated solubility regions using spectroscopic and morphological analyses.
• Varied concentration and temperature to tune solubility spheres.

Main Results:

• Identified a distinct solubility region between monomer and polymer spheres, leading to higher-order structures.
• Demonstrated that solvent polarity and side-chain interactions dictate aggregation pathways.
• Showcased the model's applicability to diverse supramolecular building blocks (triazine, Zn-porphyrin, triphenylamine).
• Confirmed that concentration and temperature influence solubility spheres.

Conclusions:

• Solvent-induced pathway complexity is a crucial factor in supramolecular polymerization.
• The Hansen solubility parameter approach provides a powerful tool for predicting and controlling self-assembly.
• Tailoring supramolecular monomer design and solvent selection is essential for targeted aggregate formation.