The Molecularly Controlled Synthesis of Ordered Bi‐dimensional C60 Arrays

Much of the research effort concerning the nanoscopic properties of clays has focused on its mechanical applications, for example, as nanofillers for polymer reinforcement. To broaden the horizon of what is possible by exploiting the richness of clays in nanoscience, herein we report a bottom‐up approach for the production of hybrid materials in which clays act as the structure‐directing interface and reaction media. This new method, which combines self‐assembly with the Langmuir–Schaefer technique, uses the clay nanosheets as a template for the grafting of C₆₀ into a bi‐dimensional array, and allows for perfect layer‐by‐layer growth with control at the molecular level. In contrast to the more‐common growth of C₆₀ arrays through nanopatterning, our approach can be performed under atmospheric conditions, can be upscaled to areas of tenths of cm², and can be applied to almost any hydrophobic substrate. Herein, we report a detailed study of this approach by using temperature‐dependent X‐ray diffraction, spectroscopic measurements, and STM.     

Large-scale controllable patterning growth of aligned organic nanowires through evaporation-induced self-assembly

Organic one-dimensional nanostructures are attractive building blocks for electronic, optoelectronic, and photonic applications. Achieving aligned organic nanowire arrays that can be patterned on a surface with well-controlled spatial arrangement is highly desirable in the fabrication of high-performance organic devices. We demonstrate a facile one-step method for large-scale controllable patterning growth of ordered single-crystal C(60) nanowires through evaporation-induced self-assembly. The patterning geometry of the nanowire arrays can be tuned by the shape of the covering hats of the confined curve-on-flat geometry. The formation of the pattern arrays is driven by a simple solvent evaporation process, which is controlled by the surface tension of the substrate (glass or Si) and geometry of the evaporation surface. By sandwiching a solvent pool between the substrate and a covering hat, the evaporation surface is confined to along the edge of the solvent pool. The geometry of the formed nanowire pattern is well defined by a surface-tension model of the evaporation channel. This simple method is further established as a general approach that is applicable to two other organic nanostructure systems. The I-V characteristics of such a parallel, organic, nanowire-array device was measured. The results demonstrate that the proposed method for direct growth of nanomaterials on a substrate is a feasible approach to device fabrication, especially to the fabrication of the parallel arrays of devices.     

A Supramolecular Photosynthetic Model Made of a Multiporphyrinic Array Constructed around a C60 Core and a C60–Imidazole Derivative

The photophysical properties of a supramolecular fullerene–porphyrin ensemble resulting from the self‐assembly of a pyrrolidinofullerene–imidazole derivative ( F1 ) with a multimetalloporphyrin array constructed around a hexasubstituted fullerene core ( F(ZnP)₁₂ ) have been investigated. The fullerene hexa‐adduct core of the host system does not play any active role in the cascade of photoinduced events of the supramolecular ensemble, indeed no intercomponent photoinduced processes could be observed in host F(ZnP)₁₂ . In contrast, upon axial coordination with the monosubstituted fullerene guest F1 , a quantitative quenching of the fluorescence signal of the metalloporphyrins was observed for the supramolecular complex [F(ZnP)₁₂(F1) _n ] both in polar and nonpolar solvents. In toluene, the supramolecular ensemble exhibits a charge transfer emission centered around 930 nm, suggesting the occurrence of intramolecular face‐to‐face interactions of F1 with neighboring metalloporphyrin moieties within the self‐assembled photoactive array. This mechanism is supported by the fact that a one order of magnitude increase in the binding constant was observed for the supramolecular complex [F(ZnP)₁₂(F1) _n ] when compared with a reference system lacking the pyrrolidinofullerene unit. In benzonitrile, a long‐lived charge‐separated state (τ=0.3 μs) has been detected for the supramolecular adduct.