Synthesis of End-Group Functionalized P3HT: General Protocol for P3HT/Nanoparticle Hybrids

Abstract

Poly(3-hexylthiophene)s were synthesized with phosphonic ester, pyridine, thiol and phenol endgroups using functionalized air-stable Ni-initiators. The protected thiol and phenol functionalized P3HTs were converted in thiol-and phenol P3HTs by quantitative postpolymerization reactions.2 1 H NMR and MALDI-ToF analysis showed very high degrees of functionalization and strong control over the polymerization except for the pyridine functionalized P3HT. These functional end-groups were used to prepare hybrid materials from a broad variety of nanoparticles, including metal oxides, quantum dots and noble metals.

Established and emerging strategies for polymer chain‐end modification

“…In particular, as KCTP is limited to bifunctional aromatic small molecules, chain‐end modification is almost the exclusive route to prepare rod‐coil block copolymers for potential applications in nanoelectronics . The Nickel catalyst can also be used as an initiator to deliver a functionalized aryl group to the α‐chain‐end and this has been exploited for the chain‐end incorporation of a range of FG, including protected alkynes, siloxanes, and alcohols …”

Protected thiol strategies in macromolecular design

“…Due to its resilience under radical conditions, the dimethyl(tert-butyl)silyl thioether has also been used for the radical polymerization of styrene [113]. In a more recent contribution, Koeckelberghs and co-workers [155] synthesized poly(3-hexylthiophene)s having varying end-groups, amongst which a thiol. This was achieved by preparing a protected thiol initiator, using a triisopropylsilyl group.…”

Morphology Control in Biphasic Hybrid Systems of Semiconducting Materials

“…Additionally, nickel catalysts were used to introduce anchor‐groups like pyridine, thiol, and phosphonic ester‐moieties . Those polymers were used for the functionalization of CdSe@ZnS, Au, or Fe 3 O 4 NCs.…”

“…This led to low P3HT content of the nanocomposites with exception of the gold NCs as estimated from FT‐IR spectra. The Au NCs were treated with thiol terminated polymers, and as thiol has a very strong affinity to gold it enables a stable functionalization even without pyridine treatment …”