Synchronous Preparation of Length-Controllable 1D Nanoparticles via Crystallization-Driven In Situ Nanoparticlization of Conjugated Polymers

Abstract

Precise size control of semiconducting nanomaterials from polymers is crucial for optoelectronic applications, but the low solubility of conjugated polymers makes this challenging. Herein, we prepared length-controlled semiconducting one-dimensional (1D) nanoparticles by synchronous self-assembly during polymerization. First, we succeeded in unprecedented living polymerization of highly soluble conjugated poly­(3,4-dihexylthiophene). Then, block copolymerization of poly­(3,4-dihexylthiophene)-block-polythiophene spontaneously produced narrow-dispersed 1D nanoparticles with lengths from 15 to 282 nm according to the size of a crystalline polythiophene core. The key factors for high efficiency and length control are a highly solubilizing shell and slow polymerization of the core, thereby favoring nucleation elongation over isodesmic growth. Combining kinetics and high-resolution imaging analyses, we propose a unique mechanism called crystallization-driven in situ nanoparticlization of conjugated polymers (CD-INCP) where spontaneous nucleation creates seeds, followed by seeded growth in units of micelles. Also, we achieved “living” CD-INCP through a chain-extension experiment. We further simplified CD-INCP by adding both monomers together in one-shot copolymerization but still producing length-controlled nanoparticles.

Modulating the Rate of Controlled Suzuki–Miyaura Catalyst-Transfer Polymerization by Boronate Tuning

“…To compare the polymerization rate of P3HT, we selected eight different boronates and monitored their SCTP rates under identical conditions by taking aliquots at specific time points. By measuring the degree of polymerization (DP) of P3HT over time and fitting the data to the first-order kinetics, 57 we obtained a high propagation rate constant k p of 4.3 × 10 −3 s −1 for the SCTP of Bpin-3HT (M1) (Table 1, entry 1, and Figure 1; see the Supporting Information (SI), page S6 for detailed kinetics). By removing the tetramethyl group, the SCTP of ethylene glycol boronate ester (Bgly)-3HT (M2) became 1.7 times faster with a measured k p of 7.3 × 10 −3 s −1 (Table 1, entry 2).…”

“…Several controlled SCTPs of thiophene, phenylene, fluorene, and carbazole monomers ,,− have been reported using pinacol boronate esters (Bpin) or cyclic triolborate salts owing to the good stability and coupling efficiency of these reagents. , However, in the SCTP of thiophene monomers, protodeboronation could not be efficiently suppressed. Recently, our group reported efficient SCTP to produce poly­(3-alkythiophene)­s (P3ATs) with excellent control and yields by combining slow-hydrolyzing MIDA boronate and a fast-initiating Buchwald RuPhos Pd G3 precatalyst. − Furthermore, we expanded the monomer scope of SCTP to strong donor, acceptor, and sterically demanding monomers by designing two new more reactive N -coordinated boronates, i.e., 4,4,8,8-tetramethyl-1,3,6,2-dioxazaborocane (Me 4 DABO) and N -benzyl-4,4,8,8-tetramethyl-1,3,6,2-dioxazaborocane ( N -BnMe 4 DABO). , Therefore, it is of interest to conduct a systematic study on the relationships between the boronate structures and their reactivity in the SCTP. Herein, we report that the rates of the SCTP of 3-hexylthiophenes (3HTs) can be modulated by tuning the boronate structure.…”

Precision Synthesis of Various Low‐Bandgap Donor–Acceptor Alternating Conjugated Polymers via Living Suzuki–Miyaura Catalyst‐Transfer Polymerization

“…Recently, our group developed an efficient SCTP system for a wide range of monomers, including strong D (3,4-[*] H. Kim, J. Lee, T. Kim, M. Cho, T.-L. Choi Department of Chemistry, Seoul National University Seoul 08826 (Republic of Korea) E-mail: tlc@snu.ac.kr propylenedioxythiophene) and A (quinoxaline, QX). [56][57][58][59] The Pd catalyst coordinated by Buchwald ligands such as RuPhos-and SPhos-Pd exhibited extraordinary catalysttransfer ability, achieving a universal polymerization of (hetero)arenes with very distinctive electronic properties by a novel strategy that included utilizing N-coordinated boronates such as 4,4,8,8-tetramethyl-1,3,6,2-dioxazaborocane (Me 4 DABO) and its N-benzylated derivative (N-BnMe 4 DABO). Therefore, this versatility encouraged us to expand the catalytic system to more challenging DA biaryl monomers.…”

“…Recently, our group developed an efficient SCTP system for a wide range of monomers, including strong D (3,4‐propylenedioxythiophene) and A (quinoxaline, QX) [56–59] . The Pd catalyst coordinated by Buchwald ligands such as RuPhos‐ and SPhos‐Pd exhibited extraordinary catalyst‐transfer ability, achieving a universal polymerization of (hetero)arenes with very distinctive electronic properties by a novel strategy that included utilizing N ‐coordinated boronates such as 4,4,8,8‐tetramethyl‐1,3,6,2‐dioxazaborocane (Me 4 DABO) and its N ‐benzylated derivative ( N ‐BnMe 4 DABO).…”

Precision Synthesis of Various Low‐Bandgap Donor–Acceptor Alternating Conjugated Polymers via Living Suzuki–Miyaura Catalyst‐Transfer Polymerization

“…Recently, our group developed an efficient SCTP system for a wide range of monomers, including strong D (3,4-propylenedioxythiophene) and A (quinoxaline, QX). [56][57][58][59] The Pd catalyst coordinated by Buchwald ligands such as RuPhos-and SPhos-Pd exhibited extraordinary catalysttransfer ability, achieving a universal polymerization of (hetero)arenes with very distinctive electronic properties by a novel strategy that included utilizing N-coordinated boronates such as 4,4,8,8-tetramethyl-1,3,6,2-dioxazaborocane (Me 4 DABO) and its N-benzylated derivative (N-BnMe 4 DABO). Therefore, this versatility encouraged us to expand the catalytic system to more challenging DA biaryl monomers.…”