Lee, Jaeho Park, Hyunwoo Hwang, Soon Hyeok Lee, In Hwan Choi, Tae Lim 2020-05-12 1520-5835 https://aurora.ajou.ac.kr/handle/2018.oak/31286 https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85084377979&origin=inward Herein, we report detailed mechanistic studies of Suzuki-Miyaura catalyst-transfer polycondensation (SCTP) of thiophene. The effects of boronates, halides, ligands, and chain transfer agents (CTAs) on the control of polymerization were systematically investigated in detail by SEC, 1H NMR and MALDI-TOF analyses. Initially, we identified that the use of the slow-hydrolyzing N-methyliminodiacetic acid (MIDA) boronate in place of conventional pinacol boronate effectively suppressed side reactions such as protodeboronation, homocoupling, and chain transfer reactions, thereby improving control of SCTP. Screening halides revealed that the monomer containing bromide was optimal for SCTP, resulting in less side reactions. Moreover, screening several ligands and adding a CTA further supported our conclusion that the RuPhos-Pd system showed the best catalyst-transfer ability among the tested catalysts. We further elucidated that externally added ligands effectively stabilized living chain-ends and suppressed chain transfer, thereby achieving controlled polymerization. We are thankful for financial support from the Creative Research Initiative Grant, the Nano-Material Technology Program, and the Beginning Independent Researcher Program through NRF, Korea. eng American Chemical Society Catalyst transfers Chain transfer agents Chain-transfer reactions Controlled polymerization Mechanistic studies Poly (3-hexylthiophene) Side reactions Suzuki-Miyaura RuPhos Pd Precatalyst and MIDA Boronate as an Effective Combination for the Precision Synthesis of Poly(3-hexylthiophene): Systematic Investigation of the Effects of Boronates, Halides, and Ligands Article 3314 9 3306 Macromolecules 53 Macromolecules, Vol.53 No.9, pp.3306-3314 10.1021/acs.macromol.0c00137 2-s2.0-85084377979 http://pubs.acs.org/journal/mamobx Article 00249297 false Organic Chemistry Polymers and Plastics Inorganic Chemistry Materials Chemistry