Unique Crystallization of Fullerenes: Fullerene Flowers

Abstract

Solution-phase crystallization of fullerene molecules strongly depends on the types of solvent and their ratios because solvent molecules are easily included in the crystal lattice and distort its structure. The C70 (solute)–mesitylene (solvent) system yields crystals with various morphologies and structures, such as cubes, tubes, and imperfect rods. Herein, using C60 and C70 dissolved in mesitylene, we present a novel way to grow unique flower-shaped crystals with six symmetric petals. The different solubility of C60 and C70 in mesitylene promotes nucleation of C70 with sixfold symmetry in the early stage, which is followed by co-crystallization of both C60 and C70 molecules, leading to lateral petal growth. Based on the growth mechanism, we obtained more complex fullerene crystals, such as multi-deck flowers and tube-flower complexes, by changing the sequence and parameters of crystallization.

Fullerene superlattices containing charge transfer complexes for an improved nonlinear optical performance

“…S5†). Previously, C 60 crystals with similar morphologies were reported by Choi et al , 3 where the crystal growth was interpreted as follows: at the initial stage, C 60 aggregated into seed crystals with a hexagonal contour followed by lateral and radial growth, and then C 60 mainly attached to the hexagonal lateral ends at the seed growth stage, resulting in a triple-deck flower-like microcrystal (Fig. 1g, bottom).…”

“…2 To date, multiple strategies have been developed to obtain C 60 -based supramolecular structures with diverse morphologies, among them a liquid–liquid interfacial precipitation (LLIP) method is frequently selected because it is easily manipulated and its structural regulation is highly capable. By varying the concentration of C 60 , 3 the diffusion time, 4 and the good-to-poor solvent ratio, 5 one-dimensional (1D) nanorods and nanotubes, 6,7 two-dimensional (2D) nanosheets, 8–11 three-dimensional (3D) microcubes 12–15 and polyhedral microcrystals 16 have been successfully synthesized. The improved orderliness of these micro/nanostructures compared to the as-synthesized C 60 powder could optimize the properties of C 60 , such as enhancing its photoluminescence.…”

Manipulating the Structural Transformation of Fullerene Microtubes to Fullerene Microhorns Having Microscopic Recognition Properties

“…As mentioned earlier, differences in the solubility of fullerenes in the good and bad solvents used influences the behaviors of self-assembled fullerene nanostructures. Fullerene C 70 has lower solubility in alcohols than C 60 so that C 70 molecules tend to form small aggregates at the early stages of crystallization from the C 60 /C 70 mixture solution . These aggregates act as a core for the further growth of cocrystals of C 60 and C 70 .…”

“…Fullerene C 70 has lower solubility in alcohols than C 60 so that C 70 molecules tend to form small aggregates at the early stages of crystallization from the C 60 /C 70 mixture solution. 54 These aggregates act as a core for the further growth of cocrystals of C 60 and C 70 . We anticipate that the solid core of the FMTs has a higher concentration of C 70 , whereas the tubular parts consist mainly of C 60 with a smaller component of C 70 (because it is already mostly crystallized at the FMT central cores).…”

Three-Dimensional “Star of David”-Shaped Fullerene (C60) Microstructures: Controlled Synthesis, Photoluminescence, and Photoelectrochemical Properties

“…5,7−16 Over the last few decades, the liquid−liquid interfacial precipitation (LLIP) method has been widely used for the facile and controllable preparation of fullerene crystals. 17,18 By choosing appropriate good/poor solvent systems and adjusting parameters such as the fullerene concentration, volume ratio of good/poor solvents, and even temperature, scientists have successfully obtained various fullerene (C 60 , C 70 , and endohedral fullerene) micro-/nanocrystals, 3,19 including onedimensional (1D) nanorods or nanotubes, 20,21 two-dimensional (2D) nanosheets and nanoflowers, 22,23 and threedimensional (3D) microcubes or micropolyhedrons. 18,24 Interestingly, all the reported fullerene micro-/nanocrystals present explicitly exposed facets.…”