Hierarchical Hybrid Nanostructures Constructed by Fullerene and Molecular Tweezer

Abstract

For the construction of well-defined hierarchical superstructures of pristine [60]fullerene (C 60 ) arrays, pyrene-based molecular tweezers (PT) were used as host molecules for catching and arranging C 60 guest molecules. The formation of host−guest complexes was systematically studied in solution as well as in the solid state. Two-dimensional proton nuclear magnetic resonance spectroscopic studies revealed that PT−host and C 60 −guest complexes were closely related to the molecular selfassembly of PT. Ultraviolet and fluorescence spectroscopic titrations indicated the formation of stable 1:1 and 2:1 (PT/C 60 ) complexes. From the nonlinear curve-fitting analysis, equilibrium constants for the 1:1 (log K 1 ) and 2:1 (log K 2 ) complexes were estimated to be 4.96 and 5.01, respectively. X-ray diffraction results combined with transmission electron microscopy observations clearly exhibited the construction of well-defined layered superstructures of the PT−host and C 60 −guest complexes. From electron mobility measurements, it was demonstrated that the welldefined hierarchical hybrid nanostructure incorporating a C 60 array exhibited a high electron mobility of 1.7 × 10 −2 cm 2 V −1 s −1 . This study can provide a guideline for the hierarchical hybrid nanostructures of host−guest complex and its applications.

Photoresponsive polymers with dangling triptycene units as efficient receptor for fullerene‐C60

“…The molecule (1) thus obtained is orange colored due to the presence of the chromophore containing the azo functional group in conjugation with two arene rings on either side. The molecule 1 was characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance ( 1 H NMR), 13 C{ 1 H} NMR and single crystal X-ray diffraction techniques. In the FTIR spectrum (supporting information Figure S1), the characteristic band due to the azo ( N═N ) functional group was observed at 1452 cm À1 .…”

“…2 This has in turn inspired a surge of research interest for the development of various host molecules, which bind efficiently with fullerene. [11][12][13][14][15][16] Additionally, the development of artificial receptors (molecular sensor and tweezers) is one of the most interesting topics of research in supramolecular chemistry. 5,12 On the other hand, triptycene has a rigid 3D structure in which three electron rich phenyl rings are oriented in a paddle wheel fashion with concave shaped cavities (Chart 1).…”

Diacetylene-Functionalized Dendrons: Self-Assembled and Photopolymerized Three-Dimensional Networks for Advanced Self-Healing and Wringing Soft Materials

“…To distinguish intramolecular and intermolecular correlations of the proton pairs, ROSEY (Figure 4) and COSY (Figure S13) spectra are examined for aDA−D and eDA−D in deuterated chloroform (c = 5.6 mM). Except for the common peaks observed in both ROSEY and COSY resulting from the intramolecular correlations, 34,35 the crosspeaks of the proton pairs, Ha(NH-CH), Hb(NH-COCH 2 ), Hc(CH-OCH 2 ), and Hd(CH 2 -OCH 2 ), only appear in the ROSEY spectra (arrows in Figure 4a). It means that crosspeaks represent the intermolecular correlations.…”

Fullerenes as Key Components for Low‐Dimensional (Photo)electrocatalytic Nanohybrid Materials

“…[36,37] Since the discovery of buckyballs by Kroto et al in 1985, [38] the first known 0D nanocarbon compound, al arge number of fullerene-based nanoheterostructures have been developed based on the unique electronaccepting properties of fullerenes,aswell as their ability to act as effective building blocks to form functional supramolecular assemblies. [39][40][41][42] Theh ybridization of fullerenes with LD na-nomaterials,s uch as quantum dots, nanoparticles,g raphene,a nd graphitic carbon nitride (g-C 3 N 4 )n anosheets,t o fabricate highly active (photo)electrocatalytic systems has notably sparked the interest of both the materials science and the catalysis communities.F ullerene-based LD hybrids have emerged as highly efficient metal-free energy conversion systems as well as potentially inexpensive alternatives to replace Pt and compete with state-of-the-art (photo)electrocatalysts,o ffering ac ombination of low cost, high activity,a nd superior stability. [43][44][45][46] Thec atalytic properties of the resulting nanohybrids are governed by their electronic structures.T he Sabatier principle states that the interactions of the reactant and intermediate species with the catalytically active surfaces should be driven by moderate energy adsorption values instead of strong or weak interfacial interactions.A ccording to this rule,the electronic behavior at the molecular level and, thus,the catalytic activity of the resulting fullerene-based LD heterostructures can be effectively tuned by engineering the morphology,composition, defect density,and strain.…”

“…Since the discovery of buckyballs by Kroto et al. in 1985, [38] the first known 0D nanocarbon compound, a large number of fullerene‐based nanoheterostructures have been developed based on the unique electron‐accepting properties of fullerenes, as well as their ability to act as effective building blocks to form functional supramolecular assemblies [39–42] . The hybridization of fullerenes with LD nanomaterials, such as quantum dots, nanoparticles, graphene, and graphitic carbon nitride (g‐C 3 N 4 ) nanosheets, to fabricate highly active (photo)electrocatalytic systems has notably sparked the interest of both the materials science and the catalysis communities.…”