Energy Landscape in Supramolecular Coassembly of Platinum(II) Complexes and Polymers: Morphological Diversity, Transformation, and Dilution Stability of Nanostructures.

Establishment of energy landscape has emerged as an efficient pathway for improved understanding and manipulation of both thermodynamic and kinetic behaviors of complicated supramolecular systems. Herein, we report the establishment of energy landscapes of supramolecular coassembly of platinum(II) complexes and polymers, as well as the fabrication of nanostructures with enhanced complexity and intriguing properties from the coassembly systems. In the energy landscape, coassembly at room temperature has been found to only allow the longitudinal growth of platinum(II) complexes and block copolymers into core-shell nanofibers that are the kinetically trapped products. Thermal annealing can switch on the transverse growth of platinum(II) complexes and block copolymers to produce core-shell nanobelts that are the thermodynamically stable nanostructures. The extents of the transverse growth are found to increase with thermal annealing temperatures, leading to nanobelts with larger widths. Besides, rapid quenching of a hot coassembly mixture to room temperature can capture intermediate nanobelt- block-nanofiber nanostructures that are metastable and capable of converting to nanobelts upon further incubation at room temperature. Moreover, sonication treatment has been found to couple with the energy landscape of the coassembly system and open a unique energy-driven pathway to activate the kinetically forbidden nanofiber-to-nanobelt morphological transformation. Furthermore, based on the established energy landscapes, nanosphere- block-nanobelt nanostructures with distinct segmented architectures have been fabricated by thermal annealing of the ternary mixture of platinum(II) complexes, block copolymers, and polymer brushes in a one-pot and single-step procedure. Finally, the nanobelts and nanosphere- block-nanobelt nanostructures are found to possess intriguing morphological stability against acid and dilution, exhibiting characteristics that are important for promising biomedical applications.