Catalyst-transfer Polycondensation Research Articles

MIDA Boronate Monomers in Suzuki–Miyaura Catalyst-Transfer Polymerization: The Pros and Cons

MIDA Boronate Monomers in Suzuki–Miyaura Catalyst-Transfer Polymerization: The Pros and Cons

Highly Efficient Preparation of Length and Width-Controllable Donor-Acceptor Nanoribbons via Polymerization-Induced Crystallization-Driven Self-Assembly of Fully Conjugated Block Copolymers.

Despite the high potential of one-dimensional (1D) donor-acceptor (D-A) coaxial nanostructures in bulk-heterojunction solar cell applications, the preparation of such 1D nanostructures using π-conjugated polymers has remained elusive. Herein, we demonstrate the first example of D-A semiconducting nanoribbons based on fully conjugated block copolymers (BCPs) prepared in a highly efficient procedure with controllable width and length via living crystallization-driven self-assembly (CDSA). Initially, Suzuki-Miyaura catalyst-transfer polymerization was employed to successfully synthesize BCPs containing two types of acceptor shells as the first block, followed by a donor poly(3-propylthiophene) core as the second block. The limited solubility and high crystallinity of the core induced a polymerization-induced crystallization-driven self-assembly (PI-CDSA) of the BCPs into nanoribbons during polymerization, providing a tunable width (7.6-39.6 nm) depending on the length of the polymer backbone. Surprisingly, purifying as-synthesized BCPs via simple precipitation directly yielded short and uniform seed structures, greatly shortening the overall protocol by eliminating the time-consuming process of initial aging and breaking down to the seed required for the conventional CDSA. With this new highly efficient method, we achieved length control over a broad range from 169 to 2210 nm, with high precision (Lw/Ln < 1.20). Furthermore, combining self-seeding and seeded growth from two different D-A-type BCPs enabled continuous living epitaxial growth from each end of the nanoribbons, resulting in B-A-B triblock D-A semiconducting comicelles with controlled length.

Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

A SNAr‐Active External Initiator that Enables Heterobifunctional Clickable Polythiophenes

AbstractPoly(3‐hexylthiophene) (P3HT) is a well‐studied conjugated polymer; however, the end‐group functionalization of these polymers is limited by fundamental synthetic challenges. Generally, end‐capping agents are used to terminate the Kumada catalyst transfer polycondensation (KCTP) to install functional end‐groups at the propagating chain end. In this work, it is shown that P3HT can be prepared with a novel SNAr‐active external initiator, followed by end capping to afford heterobifunctional end‐groups that exhibit orthogonal chemical reactivity. This orthogonal chemistry can be leveraged in sequential “click”‐type reactions to ultimately achieve the synthesis of triblock copolymers. More specifically, it is shown that the synthesis of a new pentafluorophenyl initiator allows one to append this readily functionalized group at the initiating end during P3HT synthesis. After reaching the desired degree of polymerization, an ethynyl group is incorporated at the polymer terminus using an end‐capping Grignard reagent. Critically, this heterobifunctional P3HT allows for both orthogonal para‐fluoro thiol reactions, a subset of nucleophilic aromatic substitution (SNAr), and copper‐catalyzed alkyne‐azide cycloadditions (CuAAC). The efficacy of this heterobifunctional polymer design is demonstrated by assessing sequential “click” reactions with different nonconjugated polymer blocks to either end of the P3HT polymer block.

Precision Graphene Nanoribbon Heterojunctions by Chain-Growth Polymerization.

Graphene nanoribbons (GNRs) are considered promising candidates for next-generation nanoelectronics. In particular, GNR heterojunctions have received considerable attention due to their exotic topological electronic phases at the heterointerface. However, strategies for their precision synthesis remain at a nascent stage. Here, we report a novel chain-growth polymerization strategy that allows for constructing GNR heterojunction with N=9 armchair and chevron GNRs segments (9-AGNR/cGNR). The synthesis involves a controlled Suzuki-Miyaura catalyst-transfer polymerization (SCTP) between 2-(6'-bromo-4,4''-ditetradecyl-[1,1':2',1''-terphenyl]-3'-yl) boronic ester (M1) and 2-(7-bromo-9,12-diphenyl-10,11-bis(4-tetradecylphenyl)-triphenylene-2-yl) boronic ester (M2), followed by the Scholl reaction of the obtained block copolymer (poly-M1/M2) with controlled Mn (18k) and narrow Đ (1.45). NMR and SEC analysis of poly-M1/M2 confirm the successful block copolymerization. The solution-mediated cyclodehydrogenation of poly-M1/M2 toward 9-AGNR/cGNR is unambiguously validated by FT-IR, Raman, and UV-vis spectroscopies. Moreover, we also demonstrate the on-surface formation of pristine 9-AGNR/cGNR from the unsubstituted copolymer precursor, which is unambiguously characterized by scanning tunneling microscopy (STM).

Correlating Molar Mass, π-Conjugation, and Optical Properties of Narrowly Distributed Anionic Polythiophenes in Aqueous Solutions.

Polythiophene-based conjugated polyelectrolytes (CPE) are attracting increasing attention as sensor or interface materials in chemistry and biology. While cationic polythiophenes are better understood, limited structural information is available on their anionic counterparts. Limited access to well-defined polymers has made the study of structure-property relationships difficult and clear correlations have remained elusive. By combining controlled Kumada catalyst transfer polymerization with a polymer-analog substitution, regioregular and narrowly distributed poly(6-(thiophen-3-yl)hexane-1-sulfonate)s (PTHS) with tailored chain length are prepared. Analysis of their aqueous solution structures by small-angle neutron scattering (SANS) revealed a cylindrical conformation for all polymers tested, with a length close to the contour length of the polymer chains, while the estimated radii remain too small (<1.5nm) for extensive π-stacking of the chains. The latter is particularly interesting as the longest polymer exhibits a concentration-independent structured absorption typical of crystalline polythiophenes. Increasing the ionic strength of the solution diminishes these features as the Coulomb repulsion between the charged repeat units is shielded, allowing the polymer to adopt a more coiled conformation. The extended π-conjugation, therefore, appears to be a key parameter for these unique optical features, which are not present in the corresponding cationic polythiophenes.

Living Suzuki-Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Length-Controlled Armchair Graphene Nanoribbons and Their Block Copolymers.

The bottom-up synthesis of graphene nanoribbons (GNRs) offers a promising approach for designing atomically precise GNRs with tuneable photophysical properties, but controlling their length remains a challenge. Herein, we report an efficient synthetic protocol for producing length-controlled armchair GNRs (AGNRs) through living Suzuki-Miyaura catalyst-transfer polymerization (SCTP) using RuPhos-Pd catalyst and mild graphitization methods. Initially, SCTP of a dialkynylphenylene monomer was optimized by modifying boronates and halide moieties on the monomers, affording poly(2,5-dialkynyl-p-phenylene) (PDAPP) with controlled molecular weight (Mn up to 29.8k) and narrow dispersity (Đ = 1.14-1.39) in excellent yield (>85%). Subsequently, we successfully obtained N = 5 AGNRs by employing a mild alkyne benzannulation reaction on the PDAPP precursor and confirmed their length retention by size-exclusion chromatography. In addition, photophysical characterization revealed that a molar absorptivity was directly proportional to the length of the AGNR, while its highest occupied molecular orbital (HOMO) energy level remained constant within the given AGNR length. Furthermore, we prepared, for the very first time, N = 5 AGNR block copolymers with widely used donor or acceptor-conjugated polymers by taking advantage of the living SCTP. Finally, we achieved the lateral extension of AGNRs from N = 5 to 11 by oxidative cyclodehydrogenation in solution and confirmed their chemical structure and low band gap by various spectroscopic analyses.

Recent progress on end-group chemistry of conjugated polymers based on Suzuki-Miyaura catalyst-transfer polymerization

Addition of functional groups to the end-group of conjugated polymers is key to preparing conjugated macromolecular building blocks useful for producing architecturally complex soft and hybrid conjugated materials. In this regard, the development of precision synthetic methods for conjugated polymers has paved the way for production of end-functionalized conjugated polymers in high purity. In particular, the recent advances in Suzuki-Miyaura catalyst-transfer polymerization (SCTP) have allowed access to various end-functionalized polymers due to its high polymerization efficiency under mild conditions, enhanced functional group tolerance, and improved initiation system. This review discusses the progress of end-group chemistry of conjugated polymers, focused mainly on the SCTP method.

Sequence-controlled alternating block polychalcogenophenes: synthesis, structural characterization, molecular properties, and transistors for bromine detection.

Sequence-controlled polychalcogenophenes have attracted much interest in terms of synthesis, structure and function in polymer science. For the first time, we developed a new class of alternating block conjugated copolymers denoted as poly(alt-AB)x-b-(alt-AC)y where both blocks are constituted by an alternating copolymer. 3-Hexylthiophene (S), 3-hexylselenophene (Se) and 3-hexyltellurophene (Te) are used as A, B and C units to assemble three sequence-controlled polychalcogenophenes P(SSe)b(STe), P(SSe)b(SeTe) and P(STe)b(SeTe) which are prepared by adding two different Grignard monomers in sequence to carry out Ni(dppp)Cl2-catalyzed Kumada polymerization. The molecular weight, dispersity, and length of each block (x = y) and main-chain sequence can be synthetically controlled via the catalyst transfer polycondensation mechanism. The polymer structures, i.e. alternating block main chain with high side-chain regioregularity, are unambiguously confirmed by 1H-NMR and 13C-NMR. The optical and electrochemical properties of the polymers can be systematically fine-tuned by the composition and ratio of the chalcogenophenes. From GIWAXS measurements, all the polymers exhibited predominantly edge-on orientations, indicating that the packing behaviors of the alternating block polychalcogenophenes with high regioregularity are inherited from the highly crystalline P3HT. P(SSe)b(STe) exhibited a hole OFET mobility of 1.4 × 10-2 cm2 V-1 s-1, which represents one of the highest values among the tellurophene-containing polychalcogenophenes. The tellurophene units in the polymers can undergo Br2 addition to form the oxidized TeBr2 species which results in dramatically red-shifted absorption due to the alternating arrangement to induce strong charge transfer character. The OFET devices using the tellurophene-containing polychalcogenophenes can be applied for Br2 detection, showing high sensitivity, selectivity and reversibility.

Suzuki–Miyaura catalyst-transfer polymerization: new mechanistic insights

Selective enhancement of the oxo-palladium transmetalation pathway in Ag+-mediated Suzuki–Miyaura catalyst transfer polymerization enables direct participation of N-methyliminodiacetic acid (MIDA) boronates in the polymerization process.

Tuning the emission and lighting the circularly polarized luminescence of polyfluorene by incorporating a non-emissive polycarbene

Polyfluorenes carrying a Ni(ii)-terminal were first prepared via Ni(ii)-catalyzed quasi-living Kumada catalyst-transfer polymerization, and poly(fluorene)-b-polycarbene copolymers with high optical activity and CPL were obtained in one pot.

Rethinking Catalyst Trapping in Ni-Catalyzed Thieno[3,2-b]thiophene Polymerization.

Catalyst-transfer polymerization (CTP) is a chain-growth method used to synthesize conjugated polymers. Although CTP works well for most donor-type monomers, the polymerization stalls with thieno[3,2-b]thiophene when using Ni catalysts. Previous reports have rationalized this result by suggesting that the catalyst is trapped in a Ni0 π-complex with the highly electron-rich arene. In this study, evidence is provided that the catalyst trap is more likely a NiII complex that arises from oxidative insertion of Ni0 into the C-S bonds of thieno[3,2-b]thiophene. This result is consistent with the known reactivity of Ni0 complexes toward S-heteroarenes and is supported herein by 31P nuclear magnetic resonance spectra acquired in situ, as well as data collected from small-molecule model reactions and density-functional theory simulations of the polymerization. We propose that this C-S insertion pathway and related off-cycle reactions may be relevant to understanding or enabling the CTP of other monomers with fused thiophenes.

Palladium Mediated Synthesis of Protein-Polyarene Conjugates.

Catalyst transfer polymerization (CTP) is widely applied to the synthesis of well-defined π-conjugated polymers. Unlike other polymerization reactions that can be performed in water (e.g., controlled radical polymerizations and ring-opening polymerizations), CTP has yet to be adapted for the modification of biopolymers. Here, we report the use of protein-palladium oxidative addition complexes (OACs) that enable catalyst transfer polymerization to furnish protein-polyarene conjugates. These polymerizations occur with electron-deficient monomers in aqueous buffers open to air at mild (≤37 °C) temperatures with full conversion of the protein OAC and an average polymer length of nine repeating units. Proteins with polyarene chains terminated with palladium OACs can be readily isolated. Direct evidence of protein-polyarene OAC formation was obtained using mass spectrometry, and all protein-polyarene chain ends were uniformly functionalized via C-S arylation to terminate the polymerization with a small molecule thiol or a cysteine-containing protein.

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

Herein, we demonstrate that living Suzuki-Miyaura catalyst-transfer polymerization (SCTP) using a RuPhos Pd G3 precatalyst is a versatile method for the precision synthesis of various donor-acceptor alternating conjugated polymers (DA ACPs). First, the living SCTP of biaryl monomers with combinations of both medium to strong A and D were optimized to produce DA ACPs with controlled number average molecular weight (Mn ), narrow dispersity (Ð, 1.05-1.29), and high yield (>87 %). Moreover, its expansion to controlled polymerization (Mn =9.2-40.0 kg mol-1 ) of an A1 -D-A2 -D quateraryl monomer containing diketopyrrolopyrrole (DPP; strong A) was successful. The living SCTP also enabled the efficient one-pot synthesis of various diblock and triblock copolymers. Lastly, the DA ACPs showed tunable optical band gap (Eg opt , from 1.29 to 1.77 eV) and highest occupied molecular orbital (HOMO) level (from -5.57 to -4.75 eV), while their block copolymers exhibited broad absorption ranges and promising visible light-harvesting properties.

Exploiting α-/ω-Reactivities during Polymerization for Controlled Heterotelechelic Poly(carbazole)s

The preparation of poly(N-alkyl-3,6-carbazole)s with defined α-/ω-end groups is investigated using a commercial Buchwald-type pre-catalyst. The applied excess of monofunctional aryl halide favored the Suzuki–Miyaura catalyst-transfer polymerization (SCTP) mechanism, leading to heterotelechelic polymers with defined molar masses, narrow dispersities, and high chemical yields (>85%). Notably, the absence of monofunctional aryl halide leads to quantitative formation of conjugated p-type poly(carbazole) macrocycles and the formation of longer chains via step-growth. The SCTP conditions lead to quantitative α-end group identity and up to 50% ω-end group identity due to the incomplete in situ post-polymerization capping step. The end groups were analyzed in depth by MALDI-ToF mass spectrometry on the basis of isotope simulations and relative end group distributions. The fractionation via preparative SEC yielded isolated polymer batches up to 6000 g/mol, very low dispersity values (<1.1), and confirmed end group identities (α: >99%, ω: up to 50%), including reactive azide and/or protected boronic ester end groups.

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

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

Suzuki-Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers.

Herein, we report the Suzuki–Miyaura catalyst-transfer polycondensation (SCTP) of triolborate-type carbazole monomers, i.e., potassium 3-(6-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl)triolborate (M1) and potassium 2-(7-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl) triolborate (M2), as an efficient and versatile approach for precisely synthesizing poly[9-(2-octyldodecyl)-3,6-carbazole] (3,6-PCz) and poly[9-(2-octyldodecyl)-2,7-carbazole] (2,7-PCz), respectively. The SCTP of triolborate-type carbazole monomers was performed in a mixture of THF/H2O using an initiating system consisted of 4-iodobenzyl alcohol, Pd2(dba)3•CHCl3, and t-Bu3P. In the SCTP of M1, cyclic by-product formation was confirmed, as reported for the corresponding pinacolboronate-type monomer. By optimizing the reaction temperature and reaction time, we successfully synthesized linear end-functionalized 3,6-PCz for the first time. The SCTP of M2 proceeded with almost no side reaction, yielding 2,7-PCz with a functional initiator residue at the α-chain end. Kinetic and block copolymerization experiments demonstrated that the SCTP of M2 proceeded in a chain-growth and controlled/living polymerization manner. This is a novel study on the synthesis of 2,7-PCz via SCTP. By taking advantage of the well-controlled nature of this polymerization system, we demonstrated the synthesis of high-molecular-weight 2,7-PCzs (Mn = 5–38 kg mol−1) with a relatively narrow ÐM (1.35–1.48). Furthermore, we successfully synthesized fluorene/carbazole copolymers as well as 2,7-PCz-containing diblock copolymers, demonstrating the versatility of the present polymerization system as a novel synthetic strategy for well-defined polycarbazole-based materials.

Precision Synthesis of Conjugated Polymers Using the Kumada Methodology

Since the discovery of conductive poly(acetylene), the study of conjugated polymers has remained an active and interdisciplinary frontier between polymer chemistry, polymer physics, computation, and device engineering. One of the ultimate goals of polymer science is to reliably synthesize structures, similar to small molecule synthesis. Kumada catalyst-transfer polymerization (KCTP) is a powerful tool for synthesizing conjugated polymers with predictable molecular weights, narrow dispersities, specific end groups, and complex backbone architectures. However, expanding the monomer scope beyond the well-studied 3-alkylthiophenes to include electron-deficient and complex heterocycles has been difficult. Revisiting the successful applications of KCTP can help us gain new insight into the CTP mechanisms and thus inspire breakthroughs in the controlled polymerization of challenging π-conjugated monomers.In this Account, we highlight our efforts over the past decade to achieve controlled synthesis of homopolymers (p-type and n-type), copolymers (diblock and statistical), and monodisperse high oligomers. We first give a brief introduction of the mechanism and state-of-the-art of KCTP. Since the extent of polymerization control is determined by steric and electronic effects of both the catalyst and monomer, the polymerization can be optimized by modifying monomer and catalyst structures, as well as finding a well-matched monomer-catalyst system. We discuss the effects of side-chain steric hindrance and halogens in the context of heavy atom substituted monomers. By moving the side-chain branch point one carbon atom away from the heterocycle to alleviate steric crowding and stabilize the catalyst resting state, we were able to successfully control the polymerization of new tellurophene monomers. Inspired by innocent role of the sterically encumbered 2-transmetalated 3-alkylthiophene monomer, we introduce the treatment of hygroscopic monomers with a bulky Grignard compound as a water-scavenger for the improved synthesis of water-soluble conjugated polymers. For challenging electron-deficient monomers, we discuss the design of new Ni(II)diimine catalysts with electron-donating character which enhance the stability of the association complex between the catalyst and the growing polymer chain, resulting in the quasi-living synthesis of n-type polymers. Beyond n-type homopolymers, the Ni(II)diimine catalysts are also capable of producing electron-rich and electron-deficient diblock and statistical copolymers. We discuss how density functional theory (DFT) calculations elucidate the role of catalyst steric and electronic effects in controlling the synthesis of π-conjugated polymers. Moreover, we demonstrate the synthesis of monodisperse high oligomers by temperature cycling, which takes full advantage of the unique character of KCTP in that it proceeds through distinct intermediates that are not reactive. The insight we gained thus far leads to the first example of isolated living conjugated polymer chains prepared by a standard KCTP procedure, with general applicability to different monomers and catalytic systems. In summarizing a decade of innovation in KCTP, we hope this Account will inspire future development in the field to overcome key challenges including the controlled synthesis of electron-deficient heterocycles, complex and high-performance systems, and degradable and recyclable materials as well as cutting-edge catalyst design.

Universal Suzuki-Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Strong Donor/Acceptor-Based Conjugated Polymers and Their Sequence Engineering.

Catalyst-transfer polymerization has revolutionized the field of polymer synthesis due to its living character, but for a given catalyst system, the polymer scope is rather narrow. Herein we report a highly efficient Suzuki-Miyaura catalyst-transfer polymerization (SCTP) that covers a wide range of monomers from electron-rich (donor, D) to electron-deficient (acceptor, A) (hetero)arenes by rationally designing boronate monomers and using commercially available Buchwald RuPhos and SPhos Pd G3 precatalysts. Initially, we optimized the controlled polymerization of 3,4-propylenedioxythiophene (ProDOT), benzotriazole (BTz), quinoxaline (QX), and 2,3-diphenylquinoxaline (QXPh) by introducing new boronates, such as 4,4,8,8-tetramethyl-1,3,6,2-dioxazaborocane and its N-benzylated derivative, to modulate the reactivity and stability of the monomers. As a result, PProDOT, PBTz, PQX, and PQXPh were prepared with controlled molecular weight and narrow dispersity (Đ < 1.29) in excellent yield (>85%). A detailed investigation of the polymer structures using 1H NMR and MALDI-TOF spectrometry supported the chain-growth mechanism and the high initiation efficiency of the SCTP method. In addition, the use of RuPhos-Pd showing excellent catalyst-transfer ability on both D/A monomers led to unprecedented controlled D-A statistical copolymerization, thereby modulating the HOMO energy level (from -5.11 to -4.80 eV) and band gap energy (from 1.68 to 1.91 eV) of the resulting copolymers. Moreover, to demonstrate the living nature of SCTP, various combinations of D-A and A-A block copolymers (PBTz-b-PProDOT, PQX-b-PProDOT, and PQX-b-PBTz) were successfully prepared by the sequential addition method. Finally, simple but powerful one-shot D-A block copolymerization was achieved by maximizing the rate difference between a fast-propagating pinacol boronate donor and a slow-propagating acceptor to afford well-defined poly(3-hexylthiophene)-b-poly(benzotriazole).

A Solution‐Processable Pristine PEDOT Exhibiting Excellent Conductivity, Charge Carrier Mobility, and Thermal Stability in the Doped State

AbstractPEDOT:PSS [poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate] is a widely used insoluble conducting polymer, which is therefore processed from dispersions. In this work, PEDOT homopolymers (PEDOT‐C6C8 1 and 2) highly soluble in common solvents like toluene, tetrahydrofuran, and chloroform are synthesized with a high control of molecular weight and low dispersity using Kumada catalyst transfer polymerization of a newly synthesized EDOT monomer carrying a branched alkyl substituent. Pristine PEDOT‐C6C8 allows the use in accumulation mode transistors with a high charge carrier mobility of 5 × 10−4 cm2 V−1 s−1. Moreover, these polymers can be doped in a controlled fashion, reaching conductivities of 10−3 S cm−1 at 10 mol% of a dopant, Spiro‐MeOTAD(TFSI)2. The doped state is remarkably stable, retaining 80% of the initial value after annealing under nitrogen at 100 °C and being exposed to ambient atmosphere for up to 12 h. During doping, the hole injection barrier decreases and reaches an impressively low value of 130 meV at only 2.5 mol% dopant loading without loss in carrier mobility; as monitored using ultraviolet photoelectron‐ and impedance spectroscopy. This new design concept leading to highly soluble polymers with well‐controlled molecular weights provides solution‐processable PEDOT dopable in a well‐controlled fashion.