Kinetic and Thermodynamic Aggregation of Coordinated Supramolecular Polymers with Quadruple Modulated Inversion of Circular Dichroism

Supramolecular chirality is the inherent property and the corresponding performance of aggregated materials in the supramolecular polymer (SP) system. It is an interesting but challenging issue to regulate the handedness direction of supramolecular chirality and achieve the circular dichroism (CD) inversion of chiral SP-based aggregates, especially for the ones assembled from metal-organic supramolecular polymer (MOSP) with great potential in asymmetric catalysis, chiral recognition, and chiroptical devices. Herein, a set of nanoaggregates coassembled from para-pyridine imine-linked cholesterol conjugate (pPMPCC) and various metal salts, using the cooperative interactions of metal-ion coordination, van der Waals interaction and solvent polarity, is rationally designed and prepared. Interestingly, quadruple modulated supramolecular chirality inversion (SMCI) of MOSP-based nanoaggregates is modulated by various metal ions (such as Co2+, Cu2+, Zn2+, Mn2+, and Bi3+) and their content, as well as the external stimuli like solvent effects, temperature, and ultrasound. This work provides a facile pathway to tune the helical self-aggregation of metal-organic complex systems with quadruple-modulated CD inversion, which would be of great potential in asymmetric catalysis, chiral recognition, and sensing with dynamic supramolecular chirality.

Automated summary

The circular dichroism (CD) inversion of chiral supramolecular polymer (SP) based aggregates, especially for the ones assembled from metal-organic supramolecular polymer (MOSP), has been achieved by rationally designing and preparing a set of nanoaggregates coassembled from para-pyridine imine-linked cholesterol conjugate (pPMPCC) and various metal salts. The supramolecular chirality inversion (SMCI) of these MOSP-based nanoaggregates is modulated by various metal ions and their content, as well as external stimuli like solvent effects, temperature, and ultrasound.