A facile avenue to conductive polymer brushes via cyclopentadiene–maleimide Diels–Alder ligation

Abstract

Cyclopentadienyl end-capped poly(3-hexylthiophene) was employed to fabricate conductive surface tethered polymer brushes via a facile route based on cyclopentadiene-maleimide Diels-Alder ligation. The efficient nature of the Diels-Alder ligation was further combined with a biomimetic polydopamine-assisted functionalization of surfaces, making it an access route of choice for P3HT surface immobilization.

From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes

“…Examples include the use of crosslinked or multiple-point grafted poly(glycidyl methacrylate) (PGMA) thin coatings or epoxy terminated silane SAMs to attach amine-or acid-terminated polymers [62][63][64][65][66][67][68], a reductive alkylation reaction between amine-functionalized surface and aldehyde-terminated polymers to form an imine bond which is subsequently reduced [69,70], Au-S bond formation between thiol-terminated polymer and Au surface [71,72], thiol-disulfide exchange reaction using thiol-terminated block copolymers to prepare for cleavable polymer brushes on silica particles [73,74], an amidation reaction of N-hydroxysuccinamde protected carboxylic acid terminated polymers and amine functionalized SAMs on surface [75], Diels-Alder ligation reaction between cyclopentadiene and maleimide [76], and a condensation reaction between silane-terminated polymers and silanol groups on an oxide surface [77].…”

Endo and Exo Diels–Alder Adducts: Temperature-Tunable Building Blocks for Selective Chemical Functionalization

“…Inspired by recent reports from Barner-Kowollik and co-workers, Cp end-capped polymers represent a powerful strategy for highly efficient polymer functionalization. 24–26 Indeed when P4 (see SI) and P5 were heated together in solution, a facile and catalyst-free preparation of diblock copolymer ( P6 ), with retention of the exo functionality, was achieved (Figure 5a,b). While exo protected maleimides can undergo deprotection to reveal a reactive maleimide, they can also be used for ring-opening metathesis polymerization (ROMP), 27 radical thiol-ene “click”, 28 and inverse electron-demand DA (IEDDA) reactions.…”

Metal‐Free Click Chemistry Reactions on Surfaces

“…In 2013, Yameen et al provided an elegant approach in which cyclopentadiene‐maleimide Diels‐Alder ligation was used for the fabrication of conductive polymer brushes . They used a Si substrate that was first functionalized with maleimide functional groups by employing (3‐aminopropyl)triethoxysilane (APTES) followed by reaction with 4‐maleimidobutyroyl chloride.…”