I-Fan Hsieh

Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering

The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape- and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, “giant surfactants” with precise molecular structures have been synthesized by “clicking” compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their self-assemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics.

Stoichiometric Self-Assembly of Shape-Persistent 2D Complexes: A Facile Route to a Symmetric Supramacromolecular Spoked Wheel

An approach to multicomponent coordination-driven self-assembly of the first terpyridine-based, shape-persistent, giant two-dimensional D(6h) supramacromolecular spoked wheel is reported. Mixing core T6, rim T3, and Zn(II) or Cd(II) ions in a stoichiometric ratio (1:6:12) permitted the selective generation of a highly symmetric spoked wheel in 94% isolated yield via geometric and thermodynamic control. The products were characterized by a combination of traveling-wave ion mobility mass spectrometry and NMR techniques together with TEM imaging, which agreed with computational simulations.

Phase structural formation and oscillation in polystyrene-block-polydimethylsiloxane thin films

The solvent-induced spherical structure in a polystyrene-block-polydimethylsiloxane (PS-b-PDMS) block copolymer was obtained and stabilized by preparing both the bulk and thin films from propylene glycol methyl ether acetate (PGMEA) solutions. The diblock copolymer possessed a total molecular weight of 42 kDa with a PS volume fraction of 72.2%, and it formed a cylindrical phase structure in the equilibrium bulk state. During thermal annealing, only changes in the sphere size and packing rearrangement were found. In contrast, a unique structure evolution route was observed during solvent treatments. Under a controlled vapour of a PS selective solvent, an oscillation of the structural transition between spheres and cylinders was observed in the thin films. The kinetics of this oscillation of structural transition was found to be closely related to the solvent vapour concentration and film thickness. This experiment revealed a unique ordering pathway towards the equilibrium structure in the thin film for this strongly segregated PS-b-PDMS diblock copolymer.

Phase behaviour and Janus hierarchical supramolecular structures based on asymmetric tapered bisamide

A precisely defined molecular Janus compound based on asymmetric tapered 1,4-bis[3,4,5-tris(alkan-1-yloxy)benzamido] benzene bisamide (abbreviated as C22PhBAEO3) was designed and synthesized, and its phase behavior was fully investigated. The C22PhBAEO3 compound possesses a rigid core with three aromatic rings connected with amide bonds which possess the ability to form hydrogen (H) bonds. Three hydrophobic alkyl flexible tails and three hydrophilic flexible methyl terminated triethylene glycol tails are located at the other end. Major phase transitions and their origins in C22PhBAEO3 were studied via DSC and 1D WAXD techniques. Its hierarchical supramolecular crystal structure was further identified through combined techniques of 2D WAXD and SAXS as well as SAED. Results based on computer simulations confirmed the structure determination. It was found that the C22PhBAEO3 possesses three phases through various thermal treatments including a micro-phase separated columnar liquid crystal (col.) phase, a metastable crystal I phase and a stable crystal II phase. Among them, the crystal II phase showed that the columnar structure possesses 3D inter-column order and highly crystalline alkyl tails with a long-range overall orientational order. Four C22PhBAEO3 molecules self-assembled into a phase-separated disc with an ellipsoidal shape having a C2 symmetry along the disc normal. These discs then stacked on top of each other to generate a 1D asymmetric column through H-bonding, and further packed into a 3D long-range ordered monoclinic lattice. The unit cell parameters of this lattice were determined to be a = 5.08 nm, b = 2.41 nm, c = 0.98 nm, α = 90°, β = 90°, and γ = 70.5°. The alkyl chain tails crystallize within the hydrophobic layers and possess a relatively fixed orientation with respect to the column packing due to the selective interactions based on the hydrophobic/hydrophilic microphase separation. Both phase behaviour and unit cell structure showed significant difference compared with the symmetrically tapered counterparts. The results provided a new approach of fine-tuning not only in the Janus supramolecular structures but also in the formation pathway of the self-assembling process in order to meet the specific requirements for optical and biological applications.