A Templateless Electropolymerization Approach to Nanorings Using Substituted 3,4‐Naphthalenedioxythiophene (NaPhDOT) Monomers

Abstract

The formation of highly ordered surface structures is fundamental for various applications. Due to their rapidity of implementation and their cost, templateless processes are extremely interesting alternatives to the use of templates or lithographic processes. With the aim to prepare porous structures such as nanotubes, templateless electropolymerization was found to be a unique process. Based on previous works, we have synthesized 3,4-naphthalenedioxythiophene (NaPhDOT) monomers substituted with alkyl chains (n = 2 to 10), phenyl and naphthalene substituents. In particular, NaphDOT substituted with naphthalene (NaphDOTÀNa) leads for the first time to relatively densely packed nanorings while their internal diameter is controllable with the number of deposition scans. Compared to previous works, which lead to nanotubes from non-substituted NaphDOT and 3,4-phenylenedioxythiophene substituted with naphthalene (PheDOTÀNa), with NaphDOTÀNa we observe a very important decrease in the polymer growth. As a consequence, only the initial peripherical nucleation around the gas bubbles is possible, leading to nanorings, because their growth into nanotubes is impeded by their low conductivity.

Designing bioinspired coral-like structures using a templateless electropolymerization approach with a high water content

“…The templateless deposition of metals or even of conducting polymers is an excellent alternative to obtain controllable porous nanostructures easily and quicker [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31]. In templateless electropolymerization, gas bubbles produced directly in situ during the process act as soft templates for the growth of the polymer [20][21][22][23][24][25][26][27][28][29][30][31]. In the literature, the electropolymerization of pyrrole directly in water (H 2 O) has been intensively studied [20][21][22][23][24][25][26].…”

“…By judicious use of the monomer, it is possible to obtain porous structures without surfactant. Exceptional results such as vertically aligned nanotubes were obtained with very rigid monomers such as 3,4-phenylenedioxythiophene (PheDOT), 3,4-naphthlenedioxythiophene (NaphDOT), thienothiophene derivatives and other thiophene-based monomers [21][22][23][24][25][26][27][28][29][30][31]. If the monomer is substituted, highly rigid substituents such as aromatic groups often give better results.…”

A Templateless Electropolymerization Approach to Porous Hydrophobic Nanostructures Using 3,4‐Phenylenedioxythiophene Monomers with Electron‐Withdrawing Groups

“…Recently, our group demonstrated the possibility to induce the formation of very ordered nanotubes in organic solvent such as dichloromethane and without any surfactant ,. In this process, traces of water present in solution are responsible for the nanotube formation.…”

“…The structure of the monomer used for electropolymerization was found to be extremely important because it also plays the role of a surfactant to stabilize (to fix) the gas bubbles on the surface of the polymer and to growth the polymer films around them. For example, 3,4‐(1,2‐naphtylenedioxy)( NaphDOT ) was found to be an exceptional monomer for this purpose . PheDOT monomers with different alkyl‐ and arylalkyl‐ functional groups at the benzene ring were also studied ,.…”

“…For example, 3,4‐(1,2‐naphtylenedioxy)( NaphDOT ) was found to be an exceptional monomer for this purpose . PheDOT monomers with different alkyl‐ and arylalkyl‐ functional groups at the benzene ring were also studied ,. In particular, PheDOT functionalized with a 2‐naphtylmethyl side moiety gave the best results in the growth of tubular structures ,.…”