Conjugated Polymers à la Carte from Time-Controlled Direct (Hetero)Arylation Polymerization

Morin, Pierre-Olivier; Bura, Thomas; Sun, Bin; Gorelsky, Serge I.; Li, Yuning; Leclerc, Mario

doi:10.1021/mz500656g

Cited by 104 publications

(176 citation statements)

References 33 publications

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“…These results show again that these general DHAP conditions cannot be easily applied for the coupling of nonprotected thiophene units. 12 It is also interesting to note that solid-state optical and thermal measurements seem more sensitive to the presence and detection of structural defects than 1 H NMR analyses in solution. These features could indicate that minor molecular defects can induce important changes within the supramolecular organization.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…12 Those conditions involving a palladium source, a tris(o-anisyl)-phosphine ligand, cesium carbonate, pivalic acid in toluene or THF were successfully applied to dibromo-6,6′-isoindigo derivatives as well. 13 In these cases, the resulting copolymers showed comparable, if not slightly better, properties when compared to their Suzuki-synthesized analogues.…”

Section: ■ Introductionmentioning

confidence: 99%

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En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

2015

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We report the synthesis of well-defined poly(3,3‴-didodecyl-2,2′:5′,2″:5″,2‴-quaterthiophene) (PQT12) from a direct heteroarylation polymerization (DHAP) of 5-bromo-3,3‴-didodecyl-2,2′:5′,2″:5″,2‴-quaterthiophene (monomer A) and 5-bromo-3′,4″-didodecyl-2,2′:5′,2″:5″,2‴-quaterthiophene (monomer B). Experiments with different catalysts, ligands, additives, and solvents have revealed that the utilization of Herrmann−Beller catalyst and P(oNMe 2 Ph) 3 can lead to selective thiophene−thiophene couplings. In this regard, solid-state optical and thermal measurements were particularly useful to detect the presence of β-branching and indicate that minor molecular defects can induce important changes within the supramolecular organization. We also highlight the fact that steric protection around unsubstituted β-positions of α-bromothiophene units is needed to obtain a good selectivity of the crosscouplings at the α-positions. This can be achieved by the presence of a substituent at an adjacent β-position or the utilization of a bulky acidic additive (i.e., neodecanoic acid) in the catalytic system. These synthetic procedures applied to both monomers have led to PQT12 samples showing essentially the same optical and thermal properties and are comparable to those observed with their analogues prepared from chemical oxidation or Stille coupling.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

2015

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“…This novel method allows the formation of carbon–carbon bonds between simple (hetero)arenes and (hetero)aryl halides, saving simultaneously many synthetic and tedious purification steps. Moreover, it has been shown that DHAP, when carefully optimized, can lead to improved molecular weights along with better overall yields …”

Section: Introductionmentioning

confidence: 99%

Structural Analysis of Poly(3‐hexylthiophene) Prepared via Direct Heteroarylation Polymerization

Pouliot

Wakioka

Ozawa

et al. 2016

Macro Chemistry & Physics

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This study reports the synthesis and characterization of poly(3-hexylthiophene) (P3HT) from a direct heteroarylation polymerization of two isomeric monomers, 2-bromo-3-hexylthiophene (monomer 1) and 2-bromo-4-hexylthiophene (monomer 2). Using the Herrmann-Beller catalyst along with P(o-NMe 2 Ph) 3 , the resulting polymers are obtained in excellent yields and exhibit a good number-average molecular weight (M n of 33 and 16 kDa, respectively). Detailed 1 H NMR analyses reveal less than 1% of homocouplings and no evidence of β-branching. Dehalogenation is identified as the main chain termination step and preferentially occurs on monomer 2. The melting temperature (237 °C) and hole mobility (up to 0.19 cm 2 V −1. s −1 ) of the nearly defect-free P3HT obtained from this simple polymerization of monomer 1 are comparable, if not superior, to those obtained with commercially available GRIM and Rieke samples.

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“…The polymerization conditions utilized here are based on a recent report which has shown a high selectivity between aryl-bromide and non-substituted thiophene units. [ 29 ] Suzuki cross-coupling polymerization reactions were also performed for comparison purposes (see the Supporting Information). All polymers are soluble in common chlorinated solvents, such as chloroform (CF) and o -dichlorobenzene (ODCB), as well as chlorine-free solvents such as o -xylene.…”

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New Processable Phenanthridinone‐Based Polymers for Organic Solar Cell Applications

Guérette

Najari

Maltais

et al. 2016

Advanced Energy Materials

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anionic form under the alkylation conditions. This same trend was observed for the alkylation of pyrido [2,3,4,5-lmn ]phenanthridine under basic conditions. [ 24 ] Owing to the different functional groups, M1 and M2 can be easily separated on a chromatographic column or purifi ed by recrystallization. To obtain low band gap and processable materials, these monomers were copolymerized with 2,5-bis(2-octyldodecyl)-3,6-di(thien-2-yl)pyrrolo [3,4-c ]pyrrole-1,4-dione ( M3 ) (see the Supporting Information). [ 25 ] The polymerization reactions are also described in Scheme 1 . Two alternating copolymers ( P1 and P2 ) and one random terpolymer ( P3 ) were synthesized via simple direct (hetero)arylation polymerization (DHAP) (see the Supporting Information), a "greener" method which has rapidly developed in recent years. [26][27][28] The advantages of DHAP are manifold, and include a reduction in the number of reaction steps and the elimination of toxic organometallic by-products. The polymerization conditions utilized here are based on a recent report which has shown a high selectivity between aryl-bromide and non-substituted thiophene units. [ 29 ] Suzuki cross-coupling polymerization reactions were also performed for comparison purposes (see the Supporting Information). All polymers are soluble in common chlorinated solvents, such as chloroform (CF) and o -dichlorobenzene (ODCB), as well as chlorine-free solvents such as o -xylene. Interestingly, it has been noted that P2 ( M n = 60 kDa, PDI = 4.0) always afforded higher molecular weights than P1 ( M n = 43 kDa, PDI = 4.0). This could be explained by the greater solubility of P2 . Finally, a terpolymer P3 was obtained by copolymerizing the resulting 35:65 mixture of M1 and M2 with one equivalent of M3 . With a high ratio (65%) of monomer M2 into the structure of the random terpolymer P3 , this polymer ( M n = 57 kDa, PDI = 2.9) displays a good solubility in common solvents. The electrochemical properties of the polymers were investigated by cyclic voltammetry (CV) and are reported in Figure 1 b and Table S1 (Supporting Information). The occupied and unoccupied molecular orbital (HOMO/ LUMO) levels of P1 , P2 , and P3 are −5.48/−3.93, −5.46/−3.95, and −5.43/−3.92 eV, respectively, which indicate good stability in air and similar electronic properties between polymers. As reported in Figure 1 , the pristine green polymers ( P1 , P2 , and P3 ) exhibit broad UV-vis absorption spectra with an optical band gap ( E g opt ) of 1.64-1.65 eV, which is in agreement with the measured electrochemical band gap ( E g elect = 1.51-1.55 eV). Thermogravimetric analyses revealed that all polymers are stable up to 400 °C ( Figure S11, Supporting Information). Also, differential scanning calorimetry (DSC) measurements indicate that all these non-symmetric polymers are amorphous, as no glass transition temperature is observed between 25 and 250 °C. The DSC results are corroborated by X-ray diffraction (XRD) measurements (see the Supporting Information).Organic solar cells (OSC) have attrac...

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Conjugated Polymers à la Carte from Time-Controlled Direct (Hetero)Arylation Polymerization

Cited by 104 publications

References 33 publications

En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

Structural Analysis of Poly(3‐hexylthiophene) Prepared via Direct Heteroarylation Polymerization

New Processable Phenanthridinone‐Based Polymers for Organic Solar Cell Applications

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