The Controlled Polymerization of Poly(cyclopentadithiophene)s and Their All-Conjugated Block Copolymers

Abstract

Abstract. In this manuscript, the Kumada catalyst transfer polymerization (KCTP) of cyclopenta [2,1-b;3,4-b']dithiophene (CPDT), a monomer consisting of two fused thiophene entities, is investigated. It is shown that this polymerization follows a controlled chain-growth mechanism. Furthermore, the formation of block-copolymers with poly(3-alkylthiophene)s is investigated, and it is shown that these block-copolymers can be formed if 3-alkylthiophene is used as the first block and CPDT as the second. The resulting all-conjugated block-copolymers consist of two blocks with substantially different electronic and physical properties and it is shown that the blocks influence each other, resulting in a unique material with different properties compared to a blend.2

The Influence of Substituents in the 3‐Position on the Polymerization of Metaphenylenes

“…Even though the mechanism was discovered and developed for P3AT, it was rapidly applied to several other conjugated polymers. Presently several conjugated polymers can be synthesized by KCTCP, such as poly( p ‐phenylene), poly(3‐alkylselenophene), poly( N ‐alkylpyrrole), poly(4‐alkylthiazole), poly(dithienosilole), poly(cyclopentadithiophene), poly(bithienylmethylene), and poly(fluorenes) . In 2008, Ohshimizu et al showed that the polymerization of poly(2,4‐dialkoxy‐ m ‐phenylene) using KCTCP is living.…”

“…It was also found that an alkoxy‐sidechain in the ortho ‐position hampers oxidative insertion due to its strong electron‐donating effect . Also, poly(fluorene)s, poly(cyclopentadithiophene)s, and poly(dithienosilole)s can all be polymerized in a living fashion, proving ortho ‐substituents are not necessary …”

“…Presently several conjugated polymers can be synthesized by KCTCP, such as poly(p-phenylene), poly(3-alkylselenophene), poly(N-alkylpyrrole), poly(4-alkylthiazole), poly(dithienosilole), poly(cyclopentadithiophene), poly(bithienylmethylene), and poly(fluorenes). [8][9][10][11][12][13][14][15] In 2008, Ohshimizu et al showed that the polymerization of poly(2,4-dialkoxy-m-phenylene) using KCTCP is living. The authors obtained a polymer with a remarkably converted to the monomer 3.…”

“…[7] Also, poly(fluorene)s, poly(cyclopentadithiophene)s, and poly(dithienosilole)s can all be polymerized in a living fashion, proving ortho-substituents are not necessary. [12,13,15] In this article, the polymerization of 3-alkoxy-meta-phenylenes is discussed.The authors declare no conflict of interest.…”

Gradient Sequence π-Conjugated Copolymers

“…15). This synthetic method, now known as catalyst transfer polycondensation (CTP) (13)(14)(15)(16)(17)(18)(19), paved the way for synthesizing all-conjugated diblock copolymers (20)(21)(22)(23)(24)(25)(26)(27), star polymers (28,29) and surface-grafted polymers (30)(31)(32). CTP also provides access to all-conjugated gradient sequence copolymers (33)(34)(35)(36).…”