Production of Nanostructured Conjugated Polymers by Electropolymerization of Tailored Tetrahedral Precursors

Abstract

International audience<p>3D conjugated architectures based on twisted quaterthiophene (4T) or spirobifluorene (SF) cores with 3,4-ethylenedioxythiophene (EDOT) or 3-methoxythiophene (MeOT) end-groups have been synthesized. Whereas the nature of the core has little effect on the absorption maximum of the molecule, replacement of 4T by the more rigid SF produces a large increase in the fluorescence quantum yield and a reduction in the Stokes shift accompanied by an increase in the oxidation potential. The highly reactive EDOT and MeOT end-groups allow these compounds to undergo straightforward and complete electropolymerization into stable electrode materials. Cyclic voltammetry and spectroelectrochemistry confirm the role of the precursor structure on the electrochemical properties of the polymers. Analysis of the relationships between the morphology of the polymers and the structure of the precursors, using various microscopy techniques, suggests that, with appropriate precursor design, electropolymerization can produce nanostructured electrode materials with long-range order.</p

Branched Terthiophenes in Organic Electronics: From Small Molecules to Polymers

“…The combination of a branched thiophene core with electron donating groups in the periphery was studied intensely by Roncali et al Their structures are based on a sterically twisted bithiophene node (structures 31 – 34 ) and functionalized by grafted short oligothiophene or 3,4‐ethylenedioxythiophene (EDOT) units. The electropolymerization of structures 32 – 34 will be discussed below.…”

“…The unique properties of branched all‐thiophene oligomers can also be combined with other functional monomer units as it was demonstrated by Roncali et al This group investigated a manifold of different 3,4‐ethylenedioxythiophene (EDOT) containing building blocks, amongst others branched structures incorporating the 3T unit in combination with electron donating groups . In particular three‐dimensional π‐conjugated oligothiophenes based on a twisted 2,2′‐bithiophene core derivatized with various conjugated branches containing terminal EDOT, oligothiophene or 3‐methoxythiophene end groups were shown ( 31 – 34 , Scheme ).…”

Electrochemically Generated Thin Films of Microporous Polymer Networks: Synthesis, Properties, and Applications

“…Thin films produced by this approach are generally microporous with high BET surface areas up to 2000 m 2 g −1 and low average surface roughness. A smooth surface of the films is a key prerequisite for application in organic electronic devices (e.g., OLEDs and OSCs), for long time difficult to achieve with electrogenerated conducting polymer films . Although the first paper dealing with electrogenerated, microporous films was published in 1995, the majority of reports on potential applications for this type of materials have been presented during the last three years, especially for the use in photo­­luminescence and electrochemical sensing, electrochemical supercapacitors, light‐harvesting antennae, OLEDs, and OSCs.…”

“…Another comparative study on the electropolymerization of multifunctional thiophene‐based monomers with quaterthiophene or spirobifluorene cores ( 13 and 14 ) was published by Roncali and co‐workers . Excitation and fluorescence emission spectra of monomer 14 and a related quaterthiophene‐cored monomer are depicted in Figure a.…”

“…a) Normalized PL excitation (dotted line) and emission (solid line) spectra of the rigid monomer 14 (bottom) and a semi‐rigid quaterthiophene‐cored monomer in DCM, and b) SEM and AFM images of electrogenerated films on ITO (generated under potentiostatic conditions: top: P13 ; middle: P14 ; bottom: polymer film made from the quaterthiophene‐cored monomer). Adapted with permission …”