Light-Controlled Morphologies of Self-Assembled Triarylamine–Fullerene Conjugates

Abstract

A family of triarylamine-fullerene conjugates has been synthesized and shown to self-assemble upon light stimulation in chlorinated solvents. This light-induced process primarily involves excitation of triarylamine derivatives, which then oxidize and stack with their neutral counterparts to form charge transfer complexes in the form of p-conducting channels, while fullerenes are consequently enforced in coaxial n-conducting columnar arrangements. These supramolecular heterojunctions can be organized over very long distances in micrometric fibers when a controlled amount of photons is provided from a white light source to initiate the process. Surprisingly, when sunlight or UV light is used instead, the nanostructuration leads to monodisperse spherical objects due to the nature of the nucleation-growth process involved in the stacks formation. This control over the supramolecular morphology of organic self-assemblies using the nature of light is of general interest for the design of functional responsive materials.

Unsymmetric Bistable [c2]Daisy Chain Rotaxanes which Combine Two Types of Electroactive Stoppers

“…Triarylamine 3 was prepared in three steps and excellent yields from 4‐nitro‐ N, N ‐ bis[4‐(benzyloxy) phenyl]‐phenylamine following previously described protocols of the literature , . On the other hand, N , N ‐bis(4‐(benzyloxy)phenyl) benzene‐1,4‐diamine 1 was converted into compound 2 in a good yield by a diazotization reaction using sodium nitrite in the presence of hydrochloric acid and followed by aromatic nucleophilic substitution (S N Ar) using sodium azide in deionized water (Scheme ).…”

Supramolecular Electropolymerization

“…By probing the system with UV/Vis-NIR spectroscopy,w ec onfirmed the effective photoinduced oxidation in the presence of either tetrabutylammonium perchlorate (TBAClO 4 ), tetrabutylammonium hexafluorophosphate (TBAPF 6 ), or tetrabutylammonium chloride (TBACl; see section S5.1 and Figure S5 in the Supporting Information). [13] Spectro-electrochemistry was also performed on this solution, showing the expected UV/Vis spectrum of 1C + as it passes over the first oxidation potential (Figure 1d). We then performed cyclic voltammetry (CV) at as can rate of 100 mV s À1 for 1 in TCE and in the presence of TBAPF 6 ( Figure 1c), showing the first oxidation associated with 1C + (E 1/2 = À71 mV), and as econd oxidation leading to the corresponding 1 2+ (E 1/2 = 704 mV).…”

“Click” polymerization: A convenient strategy to prepare designer fullerene materials

“…The ground state of the system was optimized using Density Functional Theory (DFT) with Becke's three parameter hybrid exchange functional and the Lee-Yange-Parr correlation functional (B3LYP) [23][24][25][26][27] with 6-31G* basis set. The vibrational frequencies were calculated to ensure that the optimized geometry corresponds to true minima on the potential energy surface [28]. The bulk solvent (chloroform) effect was included using the standard Polarizable Continuum Model (PCM) of solvation [29].…”