Influence of the Sequence in Conjugated Triblock Copolymers on Their Aggregation Behavior

Verheyen, Lize; Timmermans, Birgitt; Koeckelberghs, Guy

doi:10.1021/acs.macromol.8b01302

Cited by 18 publications

(18 citation statements)

References 23 publications

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“…cBCPs with complex architectures have been reported, such as conjugated multi-block copolymers [ 76 , 77 , 78 ], miktoarm star copolymers [ 79 , 80 , 81 , 82 , 83 ], polymer brushes [ 84 , 85 ], dendrimers [ 86 ], cyclic polymers [ 87 ], etc. Similar to binary cBCPs, polymers of other architectures can also be synthesized by using the grafting-from approach and grafting-onto approach.…”

Section: Synthesis Of Conjugated Block Copolymersmentioning

confidence: 99%

Synthesis and Self-Assembly of Conjugated Block Copolymers

et al. 2020

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In the past two decades, conjugated polymers (CPs) have drawn great attention due to their excellent conductivity and charge mobility, rendering them broad applications in organic electronics. Controlling over the morphologies and nanostructures of CPs is very important to improve the performance of CP-based devices, which is still a tremendously difficult task. Conjugated block copolymers (cBCPs), composed of different CP blocks or CP coupled with coiled polymeric blocks, not only maintain the advantages of high conductivity and mobility but also demonstrate features of morphological versatility and tunability. Due to the strong π–π interaction and crystallinity of the conjugated backbones, the self-assembly behaviors of cBCPs are very complicated and largely remain to be explored. In this tutorial review, we first summarize the general synthetic methods for different types of cBCPs. Then, recent studies on the self-assembly behaviors of cBCPs are discussed, with an emphasis on the structural factors that affect the morphologies of cBCPs both in bulk and thin film states. Finally, we briefly provide our outlook on the future research of the self-assembly of cBCPs.

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Section: Synthesis Of Conjugated Block Copolymersmentioning

confidence: 99%

Synthesis and Self-Assembly of Conjugated Block Copolymers

et al. 2020

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“…From the materials science point of view, triblock copolymers attract significant attention because of their architecture, which enables one to tune the macroscopic properties by changing the position, structure, and length of the third block [ 7 , 8 ]. In contrast to diblock copolymers, in the lamellar phase the triblock macromolecules can be in the looped and bridged configurations.…”

Section: Introductionmentioning

confidence: 99%

Liquid-Crystal Ordering and Microphase Separation in the Lamellar Phase of Rod-Coil-Rod Triblock Copolymers. Molecular Theory and Computer Simulations

et al. 2021

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A molecular model of the orientationally ordered lamellar phase exhibited by asymmetric rod-coil-rod triblock copolymers has been developed using the density-functional approach and generalizing the molecular-statistical theory of rod-coil diblock copolymers. An approximate expression for the free energy of the lamellar phase has been obtained in terms of the direct correlation functions of the system, the Flory-Huggins parameter and the Maier-Saupe orientational interaction potential between rods. A detailed derivation of several rod-rod and rod-coil density-density correlation functions required to evaluate the free energy is presented. The orientational and translational order parameters of rod and coil segments depending on the temperature and triblock asymmetry have been calculated numerically by direct minimization of the free energy. Different structure and ordering of the lamellar phase at high and low values of the triblock asymmetry is revealed and analyzed in detail. Asymmetric rod-coil-rod triblock copolymers have been simulated using the method of dissipative particle dynamics in the broad range of the Flory-Huggins parameter and for several values of the triblock asymmetry. It has been found that the lamellar phase appears to be the most stable one at strong segregation. The density distribution of the coil segments and the segments of the two different rods have been determined for different values of the segregation strength. The simulations confirm the existence of a weakly ordered lamellar phase predicted by the density-functional theory, in which the short rods separate from the long ones and are characterized by weak positional ordering.

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“…Compared to well-studied all-conjugated diblock copolymers, the synthesis of all-conjugated triblock copolymers is surprisingly limited due primarily to their relatively difficult synthesis. , An inspiring study has demonstrated to craft all-conjugated thiophene–fluorene–selenophene triblock copolymers by sequential monomer addition using the unassociated catalyst Pd(Ruphos) . Later, conjugated triblock copolymers consisting of solely thiophene units or containing thiophene and selenophene units demonstrated that when two aggregating blocks are separated by a nonaggregating block because of the large steric hindrance of the side chain, they aggregate separately, while they aggregate as one block when situated next to each other.…”

Section: Introductionmentioning

confidence: 99%

Effect of Block Sequence in All-Conjugated Triblock Copoly(3-alkylthiophene)s on Control of the Crystallization and Field-Effect Mobility

et al. 2020

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Despite recent impressive advances in synthesis of all-conjugated diblock copolymers via facile quasi-living Grignard metathesis (GRIM) polymerization, it remains challenging to achieve well-defined all-conjugated triblock copolymers of interest. Herein, we report the judicious design and synthesis of a series of all-conjugated triblock copoly(3-alkylthiophene)s consisting of poly(3-butylthiophene) (P3BT), poly(3-hexylthiophene) (P3HT), poly(3-octylthiophene) (P3OT), or poly(3-dodecylthiophene) (P3DDT) in all 12 possible combinations. The effects of block sequences and the length of alkyl side chains on their cocrystallization and microphase-separated structures are investigated. Moreover, the correlation between different crystalline structures and charge mobilities in organic field-effect transistors (OFETs) is scrutinized. These rationally synthesized triblock copoly(3-alkylthiophene)s self-assemble into cocrystals with an edge-on orientation in as-cast and 150 °C-annealed samples. Remarkably, the combinations with the shortest alkyl side chains placed as the central block (i.e., P3HT-b-P3BT-b-P3OT, P3HT-b-P3BT-b-P3DDT, P3OT-b-P3BT-b-P3DDT, and P3OT-b-P3HT-b-P3DDT) exhibit higher film crystallinity and charge mobilities than the other two combinations where the blocks with shortest alkyl side chains are located at two terminals. Intriguingly, upon thermal annealing near the melting temperature of these combinations, P3BT-b-P3OT-b-P3HT, P3BT-b-P3DDT-b-P3OT, and P3HT-b-P3DDT-b-P3OT can retain their cocrystalline structure while the other combinations are found to microphase separate. Finally, the all-conjugated triblock copoly(3-alkylthiophene)s with proper block sequence demonstrate stable charge mobilities at high temperatures and good flexibility in OFET devices. Taken together, this study elucidates that the block sequence is of key importance on control of the crystallization and charge transport behavior of poly(3-alkylthiophene)-based triblock copolymers.

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Influence of the Sequence in Conjugated Triblock Copolymers on Their Aggregation Behavior

Cited by 18 publications

References 23 publications

Synthesis and Self-Assembly of Conjugated Block Copolymers

Synthesis and Self-Assembly of Conjugated Block Copolymers

Liquid-Crystal Ordering and Microphase Separation in the Lamellar Phase of Rod-Coil-Rod Triblock Copolymers. Molecular Theory and Computer Simulations

Effect of Block Sequence in All-Conjugated Triblock Copoly(3-alkylthiophene)s on Control of the Crystallization and Field-Effect Mobility

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