Ultralarge Nanosheets Fabricated by the Hierarchical Self‐Assembly of Porphyrin‐Ended Hyperbranched Poly (ether amine) (TPP–hPEA)

Abstract

An ultralarge sheet with remarkable lateral dimensions of 10 µm × 10 µm-20 µm × 20 µm is fabricated by the hierarchical self-assembly of porphyrin-ended hyperbranched poly(ether amine) (tetraphenylporphyrin (TPP)-hPEA) in solution. The obtained TPP-hPEA amphiphiles can self-assemble from ultrathin single-layered nanosheets with a thickness of 4 nm to ultralarge multilayered nanosheets with thicknesses from 30 to 70 nm. The lateral dimensions increase from 2 × 2 µm to 5 × 5 µm, and eventually to 10 × 10 µm. In-situ dynamic light scattering and UV-vis spectroscopy studies suggest a hierarchical growth self-assembly mechanism with a self-assembly process that relies on π-π stacking. This 2D self-assembly method provides a significant potential guide for the preparation of ultralarge nanosheets in solution.

Fusion Growth of Two-Dimensional Disklike Micelles via Liquid-Crystallization-Driven Self-Assembly

“…The utilization of block copolymers with crystalline blocks is a successful method to prepare well-defined nanostructures through the crystallization-driven self-assembly (CDSA) strategy. − The key feature of this assembly process is its livingness, in which the epitaxial growth of the 2D architectures can be regulated by adding unimers to the seed solution, thus enabling control over the size of the formed structures. For example, Manners and Winnik et al successfully prepared various concentric comicelles via CDSA. − Because crystalline segments can crystallize into well-defined lattices, the formed 2D structures usually have a sharp edge. − However, manipulating 2D nanostructures through new assembly strategies is still challenging. − …”