Programmed Hierarchical Hybrid Nanostructures from Fullerene‐Dendrons and Pyrene‐Dendrons

Abstract

The construction of fullerene (C60) hierarchical nanostructures with the help of amphiphilic molecules remains a challenging task in nanoscience and nanotechnology. Utilizing the host–guest complex concept, sub‐10 nm layered superstructures are constructed from a monofunctionalized C60 dendron (C60D, guest) and tweezer‐like pyrene dendron (PD, host). Since C60D and PD are asymmetric shape amphiphiles having liquid crystal (LC) dendrons, both C60D and PD construct head‐to‐head bilayer superstructures by themselves. From fluorescence titration experiments, it is realized that the host–guest complex shows 1:1 stoichiometric binding with a binding constant (Ksv = 2.45 × 105m−1). Based on the morphological observations and scattering analyses, it is found that buckle‐like asymmetric building blocks (C60D·PD) are self‐assembled by the host–guest complex and construct multilayer hybrid nanostructures. The hierarchical hybrid nanostructures consist of the self‐assembled C60D·PD bilayer with a 2D C60·P nanoarray sandwiched between LC dendrons. This advanced strategy is expected to be a practicable and rational guideline for the fabrication of programmed hierarchical hybrid nanostructures.

Fullerene-Based Nanosurfactant for the Automatic Homeotropic Alignment of Liquid Crystals

“…According to this roughly constructed HA morphology, the host LC molecules can overcome surface anchoring and align perpendicular to the surface direction. Given the fact that C 60 D has a layer packing structure (bilayer: 7.5 nm; monolayer: 3.75 nm) consisting of a tilted building block, it is demonstrated that the majority of partially constructed protrusions consist of monolayers of C 60 D molecules, while a small number of protrusions, measuring over 4 nm, exhibit an anomalous bilayer or trilayer structure (Figure a) . The mesogen segments would be heading to the host LC medium due to LC affinity .…”

“…The C 60 D molecule was synthesized according to a previous method . The nematic liquid crystal (NLC, ZSM-7232XX, LIXON ( T ni = 75 °C, Δε = −3.4, Δ n = 0.101)), anhydrous chloroform (99%, Sigma-Aldrich), acetone (99.5%, Showa), absolute ethanol (99.5%, Sigma-Aldrich), isopropyl alcohol (99.5%, Showa), and n -hexane (99.5%, Showa) were purchased and used as received.…”

In Situ Immobilization of Palladium Nanodots in C−C Bonded 2D Conjugated Polymers through Suzuki Polymerization at the Liquid–Liquid Interface

“…Its band gap is 2.21 eV (Supporting information,F igure S3), indicating the presence of large p-conjugated system in the film. [8] Signals corresponding to Br andBcan be hardly observed, demonstrating the high conversion of the Suzuki polymerization (Figure 3d). The highresolution (HR) XPS spectrumo fC1s reveals am ajor peak of Csp 2 at 284.0 eV,w hereas other peaks ascribable to CÀO, C=O are quite weak (Figure 3d,i nset), in accordance with its highly aromatic structure.…”

Design of Surface-Aligned Main-Chain Liquid-Crystal Networks Prepared under Ambient, Light-Free Conditions Using the Diels–Alder Cycloaddition

“…MMal and MFu molecules exhibited a typical layer structure with dspacings of 1.87, 1.25, 0.74, and 0.64 nm indexed as (002), (003), (005), and (006) for MMal and d-spacings of 1.72, 1.14, 0.83, 0.67, and 0.58 nm assigned as (002), (003), (004), (005), and (006) for MFu. 27 Presumably, the (001) diffraction is not observed due to overlap with the incident beam peak. Considering the calculated length (l MMal ≈ 3.8 nm, l MFu ≈ 4.5 nm) of a molecular long axis (Figure S5), MMal monomer is expected to possess a smectic A-like structure with the observed layer spacing (L MMal ) of 3.74 nm.…”

“…To investigate the molecular packing structure of the mesogenic derivatives, one-dimensional (1D) wide-angle X-ray diffraction (WAXD) patterns were determined before and after thermal annealing at 90 °C for 10 min (Figure b). MMal and MFu molecules exhibited a typical layer structure with d -spacings of 1.87, 1.25, 0.74, and 0.64 nm indexed as (002), (003), (005), and (006) for MMal and d -spacings of 1.72, 1.14, 0.83, 0.67, and 0.58 nm assigned as (002), (003), (004), (005), and (006) for MFu . Presumably, the (001) diffraction is not observed due to overlap with the incident beam peak.…”