Ultrasmall 3D network morphologies from biobased sugar–terpenoid hybrid block co-oligomers in the bulk and the thin film states

Abstract

Nanoscale three-dimensional (3D) network morphologies, such as those represented by gyroids accessed by the self-assembly of block copolymers, are highly attractive platforms for the fabrication of nanostructured materials. However, it remains challenging to access such morphologies, especially in the sub-10 nm domain spacing region. Herein, we systematically investigated the microphase separation behaviors of biobased sugar–terpenoid hybrid block co-oligomers (BCOs) with different molecular parameters, including their volume fractions, the linker structures between the blocks, and the stereochemistries of the terpenoid blocks. The BCOs were synthesized using the azido–alkyne click reaction of propargyl-β-d-glucopyranoside with azido-functionalized farnesol, phytol, DL-α-tocopherol, and d-α-tocopherol, to ensure a well-defined molecular structure without any molecular weight distribution. Through X-ray scattering screening, we found that tocopherols, when combined with a glucose unit, yield BCOs capable of forming gyroid and hexagonally perforated lamellar (HPL) 3D network morphologies with ultrasmall domain spacings of ∼10 nm. Remarkably, HPL, which is known as a metastable phase in block copolymers, was obtained in both the bulk and film states. The nature of the linker structure and the stereochemistry of the tocopherol hydrocarbon chain were found to influence the resulting morphology and the long-range order of the nanostructures. We expect this study to contribute to the molecular design of precise block copolymers and the construction of intricate nanostructural templates with ultrasmall feature sizes.