Supramolecular Electropolymerization

Abstract

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self‐assembly and self‐organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation‐growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature.

Triphenylamine- and triazine-containing hydrogen bonded complexes: liquid crystalline supramolecular semiconductors

“…23 In this respect, it has been proven that some TPAderivatives containing amide groups aggregate in solvents to form supramolecular polymers with chirality amplification, [24][25][26][27] photoinduced self-assembly due to the formation of radical cation species in the presence of chlorinated solvents, 24,28 or supramolecular electropolymerization. 29 However, few examples have been described in which TPA is part of a mesogen that arranges in a columnar LC phase. [30][31][32][33] In addition, charge transport properties in the LC phase have not been reported to date.…”

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

“…In this paper, we describe the syntheses and the pH‐controlled contraction/extension of unsymmetric [ c 2]daisy chain rotaxanes with two different electroactive stoppers – an electron donor (Figure , blue) and an electron acceptor (red). The donor stoppers consist of triarylamine units (TAAs), and the acceptor stoppers of unsymmetrical 1,7‐dipyrrolidinyl‐substituted perylene diimides (PDIs) . This interlocked structure presents two molecular stations – an ammonium group (orange in Figure ) and a triazolium group (purple in Figure ) – with different affinities for the macrocycle.…”

Supramolecular Polymeric Radicals: Highly Promoted Formation and Stabilization of Naphthalenediimide Radical Anions

“…Supramolecular polymers refer to polymers in which monomers are connected with each other via noncovalent interactions. [38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57] We wondered if organic radicals could be noncovalently linked together to form well-organized supramolecular polymeric radicals. In this way, the modulation effect on the activity of radicals may be significantly amplified through the combination of multiple noncovalent interactions and the rigid and bulky structure of supramolecular polymers.…”