3D-Conformer of Tris[60]fullerenylated cis-Tris(diphenylamino-fluorene) as Photoswitchable Charge-Polarizer on GHz-Responsive Trilayered Core-Shell Dielectric Nanoparticles

Abstract

Novel 3D-configurated stereoisomers cis-cup-tris[C60>(DPAF-C9)] and trans-chair-tris[C60>(DPAF-C9)] were designed and synthesized in good yields. The former, with three C60> cages per molecule facing at the same side of the geometrical molecular cup-shape, was proposed to provide excellent binding interaction forces at the gold surface of core-shell γ-FeOx@AuNP nanoparticles and to direct the subsequent formation of a fullerene cage array (defined as fullerosome). Upon photoactivation of the Au-layer and cis-cup-tris[C60>(DPAF-C9)] itself, the degree of photoinduced intramolecular e−-transfer from DPAF to a C60> moiety was found to be largely enhanced by the accumulated plasmonic resonance energy at the near-field surface. Distribution of resulting negative charges along the outer (C60>)-derived fullerosome shell layer of the trilayered NPs was correlated with the detected photoswitchable dielectric amplification phenomena using white LED light at 1.0 GHz.

Materials Chemistry of Fullerenes, Graphenes, and Carbon Nanotubes

“…Two interesting modifications both involved 3D-conformeric C 60 (>DPAF-C 9 ) derivatives by fusing three phenyl rings of three diphenylamino groups together to form a shared central benzene moiety as the base of 3D configuration design. Specifically, the successful synthesis of cis-cup-tris[(DPAF-C 2M )-C 60 (>DPAF-C 9 )] stereoisomer may beneficial for use as positive (DPAF-C n ) + and negative charge (<C 60 >) − carriers in enhancing photoinduced dielectric characteristics [43]. It can also be applied as the precursor building block in the synthesis of several C 60 -and C 70 -based ultrafast photoresponsive nonlinear two-photon absorptive nanomaterials.…”

“…Flakes obtained from direct exfoliation of graphite (e.g., by liquid phase exfoliation [6,7]) have more regular structure and better conductive properties, and are therefore more suitable for electronics applications, but are also more expensive and difficult to obtain and handle. Therefore, for the 3D scaffold building, usually, the process starts from the oxidation of graphite to graphite oxide, e.g., by Hummer's method [38], followed by exfoliation-reduction either thermally [39], leading to Thermal Exfoliate Graphite Oxide (TEGO), or using microwaves, leading to Microwave Exfoliate Graphite Oxide (MEGO) [40,41], resulting in materials with SSA usually not exceeding 800 m 2 /gr [42,43]. Samples can be subject to additional treatments, such as further reduction, or chemical activation (e.g., with KOH), which modify the edges with the result of increasing the porosity to specific pore volume (SPV) greater than 2 cm 3 /g [30,44] and improving the SSA up or exceeding the graphene limit (2630 m 2 /g).…”

“…Mostly, CNT of type PR-24-XT-HHT (Pyrograf Products, Inc., Cedarville OH, USA) have been used as templates. For introducing materials into the inner cavity of the CNT, mainly extensions of solution-based approaches reported in [38][39][40][41][42][43] have been applied [44,45]. This is illustrated by the example of Mn 3 O 4 @CNT which has been obtained by filling CNT with a manganese salt solution and a subsequent reducing step yielding homogeneously MnO-filled CNT (MnO@CNT) [4].…”

“…Each approach shows peculiar features in terms of chemical compatibility, reaction conditions, and derivatization degree [43,44], which can be finely tuned according to the specific application needs (Figure 2). In all cases, intermediate species with high chemical versatility are obtained, with further derivatization processes allowing the fabrication of functional materials for cancer therapy [90].…”

Synthesis and Intramolecular Energy- and Electron-Transfer of 3D-Conformeric Tris(fluorenyl-[60]fullerenylfluorene) Derivatives

“…Two interesting modifications both involved 3D-conformeric C 60 (>DPAF-C 9 ) derivatives by fusing three phenyl rings of three diphenylamino groups together to form a shared central benzene moiety as the base of 3D configuration design. Specifically, the successful synthesis of cis - cup -tris[(DPAF-C 2M )-C 60 (>DPAF-C 9 )] stereoisomer may be beneficial for use as positive (DPAF-C n ) + and negative charge (<C 60 >) − carriers in enhancing photoinduced dielectric characteristics [43]. It can also be applied as the precursor building block in the synthesis of several C 60 - and C 70 -based ultrafast photoresponsive nonlinear two-photon absorptive nanomaterials.…”