End Group Modification of Regioregular Polythiophene through Postpolymerization Functionalization

Abstract

HT-poly(3-hexylthiophenes) (HT-PHT) with H/Br end group composition were prepared via a modified McCullough method using anhydrous ZnCl2 for the transmetalation step. These bromineterminated HT-PHT can be end group modified at the ω end through a cross-coupling reaction with thienylzinc compounds bearing a THP-protected hydroxy or STABASE-protected amino groups. After deprotection, HT-PHTs with -OH or -NH2 functional groups at the ω end were obtained. In addition, HT-PHT with pure H/H end group composition were also modified by treatment with Vilsmeier reagent and functionalized with formaldehyde groups at both the R and ω chain ends. Reduction of the formaldehyde groups produced the HT-PHT diol. MALDI-TOF is a powerful tool to monitor each step of these end group functionalizations.

Synthesis and Characterization of Poly(3-hexylthiophene)-b-Polystyrene for Photovoltaic Application

“…After the column chromatography, purity of monobromo thiophene increased to 99.3%. P3HT with a bromo terminal (P3HT-Br; 5) was synthesized by Grignard metathesis polymerization according to reference [24]. The M n and PDI were determined by GPC as 8,100 and 1.49, respectively.…”

“…Regioregular poly(3-hexylthiophene) with bromo group at a terminal (P3HT-Br, 5) were prepared by the modified method previously reported [24]. A flask equipped with a stopcock was charged with 130 mL of distilled THF and cooled down to −78 °C.…”

“…Since the coupling reactions do not require severe conditions, it is possible to introduce a variety of non-P3HT building blocks [23]. Since Grignard metathesis polymerization of 2-bromo-3-hexylthiophene exclusively affords polymer chains terminated with a proton at one end and a bromine at the other end [24], no further chemical modification is necessary for P3HT to obtain diblock copolymers.…”

End-group stannylation of regioregular poly(3-hexylthiophene)s

“…On the other hand, even though the post-functionalization of purified P3HT has certain drawbacks, such as lower introduction rate and selectivity, it is free from the limitations of functionalities and can be used to functionalize both ends of chains. [10][11][12] Taking advantage of this, reactive groups such as carboxylic acids 10,11 and aldehydes 12 have been introduced into the ends of P3HT by post-functionalization. However, this approach has been relatively less studied.…”

Preparation of nanocrystals and nanocomposites of nanocrystal-conjugated polymer, and their photophysical properties in confined geometries

“…TOPO-covered CdTe short nanorods (7 nm in diameter and 20 nm in length; Supporting Information) and TOPO-covered Au nanoparticles (6 nm in diameter) were also synthesized and purified in accordance with previous reports. 33,34 Pattern formation in the sphere-on-flat geometry: A drop of a solution of nanoparticles in toluene (12 L; CdSe/ZnS QDs, CdTe nanorods or Au nanoparticles) was loaded in a small gap between a spherical silica lens and a SiO 2 -coated Si wafer (thermally coated 300 nm thick SiO 2 on Si). The sphere and Si wafer were firmly fixed at the top and bottom, respectively, of a sample holder inside a sealed chamber.…”