Abstract
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.
Highlights
Discrete block co-oligomers (BCOs) are gaining considerable attention due to their potential to form highly ordered ultrasmall nanostructures suitable for lithographic templates
Proton nuclear magnetic resonance (1H NMR) spectra were assigned to the expected BCO chemical structure (Supplementary Figs. 2–8), and the size-exclusion-chromatography (SEC; in DMF containing 0.01 M LiCl) elution peak clearly shifted toward the highermolecular-weight region upon increasing the number of glucose units in the BCO (Fig. 2a)
We reported the development of a readily available monodisperse and discrete block co-oligomer (BCO) system consisting of hydrophilic sugars and hydrophobic terpenoids
Summary
Discrete block co-oligomers (BCOs) are gaining considerable attention due to their potential to form highly ordered ultrasmall nanostructures suitable for lithographic templates. Click coupling of propargylfunctionalized 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. We employ a series of sugars from monosaccharide (i.e., glucose) to heptasaccharide (i.e., maltoheptaose) as oligosaccharide blocks, while farnesol (3,7,11-trimethyldodeca-2,6,10-trien-1-ol; mixture of isomers), DL-α-tocopherol (2,5,7,8-tetramethyl-2-[(4,8,12trimethyltridecyl)]chroman-6-ol), and solanesol ((2E,6E, 10E,14E,18E,22E,26E,30E)-3,7,11,15,19,23,27,31,35-nonamethylhexatriaconta-2,6,10,14,18,22,26,30,34-nonaen-1-ol)—which are a family of terpenoids containing three, four, and nine isoprene units, respectively—are selected as hydrophobic blocks Using this BCO system, we attempt the construction of LAM, GYR, and hexagonally close-packed cylindrical (HEX) morphologies by adjusting the DP of each block, and the d values of the resulting organic-BCP/BCO-based microphase-separated structures are examined
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