Discrete block co-oligomers (BCOs) are gaining considerable attention due to their potential to form highly ordered ultrasmall nanostructures suitable for lithographic templates. However, laborious synthetic routes present a major hurdle to the practical application. Herein, we report a readily available discrete BCO system that is capable of forming various self-assembled nanostructures with ultrasmall periodicity. Click coupling of propargyl-functionalized sugars (containing 1–7 glucose units) and azido-functionalized terpenoids (containing 3, 4, and 9 isoprene units) afforded the discrete and monodisperse BCOs with a desired total degree of polymerization and block ratio. These BCOs microphase separated into lamellar, gyroid, and cylindrical morphologies with the domain spacing (d) of 4.2–7.5 nm. Considering easy synthesis and rich phase behavior, presented BCO systems could be highly promising for application to diverse ~4-nm nanofabrications.

离散嵌段共聚低聚物 (BCO) 因其形成适用于光刻模板的高度有序的超小纳米结构的潜力而受到广泛关注。然而，费力的合成路线是实际应用的主要障碍。在此，我们报告了一种现成的离散 BCO 系统，该系统能够形成各种具有超小周期性的自组装纳米结构。炔丙基功能化糖（包含 1-7 个葡萄糖单元）和叠氮基功能化萜类化合物（包含 3、4 和 9 个异戊二烯单元）的点击偶联为离散和单分散 BCO 提供了所需的总聚合度和嵌段比。这些 BCOs 微相分离为层状、螺旋状和圆柱状形态，畴间距为 ( d) 为 4.2–7.5 纳米。考虑到易于合成和丰富的相行为，所提出的 BCO 系统非常有希望应用于各种 ~4 纳米纳米加工。