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Title:
FLUORINATED DITHIENYL-DIKETOPYRROLOPYRROLE MONOMERS AND POLYMERS AND USES THEREOF
Document Type and Number:
WIPO Patent Application WO/2019/041047
Kind Code:
A1
Abstract:
Fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers are disclosed herein. More specifically, fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers for use in organic electronics are disclosed. A process for the preparation of fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers is also disclosed. The fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers are characterized by high electron mobility, high hole mobility and good power conversion efficiencies.

Inventors:
LECLERC, Mario (909 rue Laudance, Apt. 316Québec, Québec G1X 5H7, G1X 5H7, CA)
BURA, Thomas (272 9e rue, Québec, Québec G1L 2N2, G1L 2N2, CA)
BEAUPRÉ, Serge (1150 rue de Constance, Québec, Québec G1Y 1K2, G1Y 1K2, CA)
Application Number:
CA2018/051056
Publication Date:
March 07, 2019
Filing Date:
August 31, 2018
Export Citation:
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Assignee:
UNIVERSITÉ LAVAL (Vice-Rectorat à la Recherche et à la Création, Pavillon des Sciences de l'Éducation2320 rue des Bibliothèque, Québec Québec G1V 0A6, G1V 0A6, CA)
International Classes:
C08G61/12; C07F7/14; H01L51/30; H01L51/46
Foreign References:
CN103012751A2013-04-03
Other References:
SHEN, LI: "Effects of aromatic substituents on the electronic structure and excited state energy levels of diketopyrrolopyrrole derivatives for singlet fission", PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 20, no. 35, 2018, pages 22997 - 23006, XP055579280
BURA, THOMAS: "New Fluorinated Dithienyldiketopyrrolopyrrole Monomers and Polymers for Organic Electronics", MACROMOLECULES, vol. 50, no. 18, 15 September 2017 (2017-09-15), pages 7080 - 7090, XP055579287
Attorney, Agent or Firm:
BENOÎT & CÔTÉ INC. (560 Cremazie Blvd. East, Suite 300Montréal, Québec H2P 1E8, H2P 1E8, CA)
Download PDF:
Claims:
CLAIMS

1. A polymer comprising a repeating unit of the formula:

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least one of R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1.

2. The polymer of claim 1, wherein Ar1 and Ar2 are independently selected mono or polycyclic heteroarenes or arenes.

3. The polymer of claim 1 or 2, wherein Ar1 is

wherein R is an alkyl group and wherein The polymer of claim 1 or 2, wherein Ar

wherein R1 and R2 are independently selected alkyl groups, and wherein The polymer of claim 1 or 2, wherein Ar1 is

wherein y is 0.

The polymer of claim 1 or 2, wherein Ar

wherein R is an alkyl group and wherein y is 0.

7. The polymer of claim 1 or 2, wherein the repeating unit has the structure

8. The polymer of claim 1 or 2, wherein the repeating unit has the structure

9. The polymer of claim 1 or 2, wherein the repeating unit has the structure

The polymer of claim 1 or 2, wherein the repeating unit has the structure The polymer of claim 1 or 2, wherein the repeating unit has the structure

The polymer of claim 1 or 2, wherein the repeating unit has the structure

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and y is 0 or 1.

The copolymer of claim 13, wherein Ar1 and Ar2 are independently selected polycyclic heteroarenes or arenes.

The copolymer of claim 13 or 14, wherein a first Ar

and a second Ar is

wherein R is an alkyl group and wherein

The copolymer of claim 15, wherein the repeating unit has the structure

The copolymer of claim 15, wherein the repeating unit has the structure

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least one of R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1.

The polymer of claim 18, wherein Ar1 and Ar2 are independently selected mono or polycyclic heteroarenes or arenes. A copolymer comprising at least one repeating unit of the formula:

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least one of R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1.

21. The polymer of claim 20, wherein Ar1 and Ar2 are independently selected mono or polycyclic heteroarenes or arenes.

22. An organic semiconductor material, layer or component, comprising a polymeric material as defined in any one of claims 1 to 21.

23. An electronic device, comprising a polymeric material as defined in any one of claims 1 to 21.

24. The electronic device of claim 23, wherein the device is an organic photovoltaic device, a photodiode or an organic filed effect transistor.

25. Use of the polymeric material as defined in any one of claims 1 to 21 as an organic semiconductor material, layer or component.

26. Use of the polymeric material as defined in any one of claims 1 to 21 in an electronic device.

27. The use of claim 26, wherein the device is an organic photovoltaic device, a photodiode or an organic filed effect transistor.

28. A monomer having the formula:

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least one of R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1.

The polymer of claim 1, wherein Ar1 and Ar2 are independently selected mono or polycyclic heteroarenes or arenes.

A monomer having the formula:

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least one of R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1.

31. The monomer of claim 30, wherein Ar1 and Ar2 are independently selected mono or polycyclic heteroarenes or arenes.

32. The monomer of claim 30 or 31, having the structure:

The monomer of claim 30 or 31, having the structure:

The monomer of claim 30 or 31, having the structure:

The monomer of claim 30 or 31, having the structure:

The monomer of claim 30 or 31, having the structure:

The monomer of claim 30 or 31, having the structure:

The monomer of claim 30 or 31, having the structure:

wherein

R1, R2 and R7 are independently selected alkyl groups. The monomer of claim 30 or 31, having the structure:

wherein

R1 and R2 are independently selected alkyl groups. 40. An oligomer comprising at least one repeating unit of the formula:

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1. An oligomer comprising at least one repeating unit of the formula:

wherein

R1 and R2 are independently selected alkyl groups;

R3, R4, R5 and R6 are independently selected from H and F, such that at least one R3 and R4 is F, and such that at least one of R5 and R6 is F;

Ar1 and Ar2 are independently selected electron donating units;

x is 0 or 1 ; and

y is 0 or 1.

A process for preparing 4-fluoro-2-thiophenecarbonitrile comprising reacting compound of formula I with an organolithium reagent and a fluorinating agent to obtain a compound of formula II wherein Ai, A2 and A3 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl or cycloalkyl. The process of claim 42, wherein the compounds of formula I and II have the structures

respectively.

44. The process of claim 42 or 43, wherein the organolithium reagent is «-BuLi.

45. The process of any one of claims 42 to 44, wherein the fluorinating agent is reagent is NFSI.

46. The process of claim 45, wherein the NFSI is recrystallized prior to use.

47. The process of any one of claims 42 to 46, further comprising the use of TMEDA.

48. The process of any one of claims 42 to 47, wherein the reaction is carried out at - 100°C.

49. A process for preparing 4-fluoro-5-alkylsilyl-2-thiophenecarbonitrile comprising reacting a compound of formula I with an organolithium reagent and a fluorinating agent to obtain a compound of formula II and reacting the compound of formula II with an organolithium reagent and a cyanating agent to obtain a compound of formula III wherein Ai, A2 and A3 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl or cycloalkyl.

The process of claim 49, wherein the compounds of formula I, II and II have the structures

respectively.

51. The process of claim 49 or 50, wherein the organolithium reagent is at least one of n- BuLi or t-BuLi.

52. The process of any one of claims 49 to 51, wherein the fluorinating agent is reagent is NFSI.

53. The process of claim 52, wherein the NFSI is recrystallized prior to use.

54. The process of any one of claims 49 to 53, wherein the cyanating agent is phenyl cyanate.

55. The process of any one of claims 49 to 54, wherein the reaction is carried out at - 80°C.

Description:
TITLE

FLUORINATED DITHIENYL-DIKETOPYRROLOPYRROLE MONOMERS AND

POLYMERS AND USES THEREOF

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application 62/552,759, filed August 31, 2017. The contents of the referenced application are incorporated into the present application by reference.

FIELD

[0002] The present disclosure broadly relates to electroactive and photoactive polymers. More specifically but not exclusively, the present disclosure relates to fluorinated electroactive and photoactive polymers. Yet more specifically but not exclusively, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole- based polymers. The present disclosure also relates to a process for the preparation of fluorinated dithienyl-diketopyrrolopyrrole-based polymers. Moreover, the present disclosure relates to the use of fluorinated dithienyl-diketopyrrolopyrrole-based polymers in organic electronics.

BACKGROUND

[0003] In the past few years, organic solar cells (OSCs) and organic field-effect transistors (OFETs) based on π-conjugated polymers have stimulated broad interest from both academic and industrial laboratories due to the possibility of creating efficient, lightweight and flexible devices using inexpensive and environmentally friendly solution- based printing techniques.

[0004] Tuning of the physical and electro-optical properties of conjugated polymers through chemical modification of their backbone has led to a wide array of promising materials for organic electronics applications. Indeed, with polymer solar cells (PSC) with power conversion efficiencies (PCE) exceeding 10%, OFETs with hole mobilities up to 20 cm 2 V "1 s "1 and electron mobilities as high as 7.0 cm 2 V "1 s "1 , conjugated polymers now show performances suitable for commercial applications.

[0005] Among all the new electroactive and photoactive materials developed over the past 20 years, 2,5-dihydropyrrolo[3,4-c]pyrrole-l ,4-dione (DPP) based polymers have been found especially valuable since they deliver high efficiencies in both PSCs and OFETs. For example, PDPPTT, a copolymer made from dithienyl-DPP and thieno[3,2-6]thiophene (TT), showed a PCE up to 9.4% and a hole mobility up to 10.5 cm 2 V "1 s "1 .

[0006] Since the first report on the synthesis of 3,6-diphenyl-DPP, the synthesis and the modulation of the electro-optical properties of DPP copolymers have been extensively studied and reviewed. Indeed, the flanking aromatic substituents (e.g. five- or six- membered-fused or non-fused heterocyclic rings) strongly modulate the electro-optical properties. Flanking thiophenes, notably have minimal steric effects on the DPP core and lead to co-planar dithienyl-DPP building blocks that are widely used in the synthesis of polymers.

[0007] Recently, fluorination of the conjugated backbone of D-A (donor-acceptor) copolymers has proven to be effective to enhance the performance of PSCs and OFETs. ^ The strong electronegativity of fluorine effectively lowers both the HOMO and LUMO energy levels of the fluorinated copolymers without perturbing the planarity of the backbone, thanks to its small van der Waals radius (r = 0.135 nm). In addition, changes in crystallinity, internal polarization and changes in the morphology of the active layer have also been attributed to fluorination. The effect of the fluorine atom on the performance of semiconducting polymers has been recently discussed. [2"6]

SUMMARY

[0008] The present disclosure broadly relates to electroactive and photoactive polymers. More specifically but not exclusively, the present disclosure relates to fluorinated electroactive and photoactive polymers. Yet more specifically but not exclusively, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole- based polymers. The present disclosure also relates to a process for the preparation of fluorinated dithienyl-diketopyrrolopyrrole-based polymers. Moreover, the present disclosure relates to the use of fluorinated dithienyl-diketopyrrolopyrrole-based polymers in organic electronics.

[0009] In an embodiment, the present disclosure relates to fluorinated dithienyl- diketopyrrolopyrrole-based polymers. In a further embodiment, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole-based copolymers. In a further embodiment, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole- based polymers and copolymers having high electron mobility. In a further embodiment, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers having high hole mobility. In a further embodiment, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers having power conversion efficiencies (PCE) exceeding 7%. In a further embodiment, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers for use in organic electronics. In an aspect of the present disclosure, the organic electronics include photovoltaic devices (e.g. solar cells), field effect transistors and light-emitting diodes.

[0010] In an embodiment, the present disclosure relates to fluorinated dithienyl- diketopyrrolopyrrole. In a further embodiment, the present disclosure relates to fluorinated dithienyl-diketopyrrolopyrrole and derivatives thereof.

[0011] In an aspect, the present disclosure relates to a polymer having a repeating unit of the formula:

wherein:

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and;

y is 0 or 1.

[0012] In an embodiment of the present disclosure, Ar 1 and Ar 2 are independently selected mono or polycyclic heteroarenes or arenes. In a particular embodiment of the present disclosure Ar 1 is wherein R is an alkyl group. In a particular embodiment of the present disclosure Ar is

wherein R 1 and R 2 are independently selected alkyl groups. In a particular embodiment of the present disclosure, Ar 1 is a particular embodiment of the present disclosure, Ar

wherein R is an alkyl group.

[0013] In a particular embodiment, the present disclosure relates to a polymer having a repeating unit of the formula:

[0015] In a particular embodiment, the present disclosure relates to a polymer having a repeating unit of the formula:

[0016] In a particular embodiment, the present disclosure relates to a polymer having a repeating unit of the formula:

[0017] In a particular embodiment, the present disclosure relates to a polymer having a repeating unit of the formula:

[0018] In a particular embodiment, the present disclosure relates to a polymer having a repeating unit of the formula:

[0019] In an aspect, the present disclosure relates to a copolymer having at least one repeating unit of the formula:

wherein:

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and;

y is 0 or 1.

[0020] In an embodiment of the present disclosure, Ar 1 and Ar 2 are independently selected mono or polycyclic heteroarenes or arenes. In a particular embodiment of the present disclosure a first Ar 1 is

and a second Ar is

wherein R is an alkyl group.

[0021] In a particular embodiment, the present disclosure relates to a copolymer having a repeating unit of the formula:

[0022] In a particular embodiment, the present disclosure relates to a copolymer having a repeating unit of the formula:

[0023] In an aspect, the present disclosure relates to a polymer having a repeating unit of the formula:

wherein:

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and

y is 0 or 1.

[0024] In an embodiment of the present disclosure, Ar 1 and Ar 2 are independently selected mono or polycyclic heteroarenes or arenes.

[0025] In an aspect, the present disclosure relates to a copolymer having at least one repeating unit of the formula:

wherein:

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and

y is 0 or 1.

[0026] In an embodiment of the present disclosure, Ar 1 and Ar 2 are independently selected mono or polycyclic heteroarenes or arenes.

[0027] In an aspect, the present disclosure relates to an organic semiconductor material, layer or component, comprising a fluorinated polymer or copolymer in accordance with the present disclosure.

[0028] In an aspect, the present disclosure relates to an electronic device, comprising a fluorinated polymer or copolymer in accordance with the present disclosure. In a particular embodiment of the present disclosure, the electronic device is an organic photovoltaic device, a photodiode or an organic filed effect transistor.

[0029] In an aspect, the present disclosure relates to the use of a fluorinated polymer or copolymer in accordance with the present disclosure as an organic semiconductor material, layer or component.

[0030] In an aspect, the present disclosure relates to the use of a fluorinated polymer or copolymer in accordance with the present disclosure in an electronic device. In a particular embodiment of the present disclosure, the electronic device is an organic photovoltaic device, a photodiode or an organic filed effect transistor.

[0031] In an aspect, the present disclosure relates to a monomer having the formula:

wherein

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and

y is 0 or 1.

[0032] In an embodiment of the present disclosure, Ar 1 and Ar 2 are independently selected mono or polycyclic heteroarenes or arenes.

[0033] In an aspect, th present disclosure relates to a monomer having the formula:

wherein

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and

y is 0 or 1.

[0034] In an embodiment of the present disclosure, Ar 1 and Ar 2 are independently selected mono or polycyclic heteroarenes or arenes.

[0035] In a particular embodiment, the present disclosure relates to a monomer having the structure:

a particular embodiment, the present disclosure relates to a monomer having

[0037] In a particular embodiment, the present disclosure relates to a monomer having the structure:

[0038] In a particular embodiment, the present disclosure relates to a monomer having the structure:

[0039] In a particular embodiment, the present disclosure relates to a monomer having the structure:

[0040] In a particular embodiment, the present disclosure relates to a monomer having the structure:

a particular embodiment, the present disclosure relates to a monomer having

wherein:

R 1 , R 2 and R 7 are independently selected alkyl groups.

[0042] In a particular embodiment, the present disclosure relates to a monomer having the structure:

wherein:

R 1 and R 2 are independently selected alkyl groups.

[0043] In an aspect, the present disclosure relates to an oligomer having at least one repeating unit of the formula:

wherein: R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and

y is 0 or 1.

[0044] In an aspect, the present disclosure relates to an oligomer having at least one repeating unit of th formula:

wherein:

R 1 and R 2 are independently selected alkyl groups;

R 3 , R 4 , R 5 and R 6 are independently selected from H and F, such that at least one of R 3 and R 4 is F, and such that at least one of R 5 and R 6 is F;

Ar 1 and Ar 2 are independently selected electron donating units; x is 0 or 1 ; and

y is 0 or 1.

[0045] In an aspect, the present disclosure relates to pure 4-fluoro-2- thiophenecarbonitrile .

[0046] In an aspect, the present disclosure relates to a process for preparing fluorinated dithienyl-diketopyrrolopyrrole-based polymers and copolymers. In an embodiment of the present disclosure, the process comprises polymerizing fluorinated dithienyl- diketopyrrolopyrrole. In a further embodiment of the present disclosure, the process comprises polymerizing fluorinated dithienyl-diketopyrrolopyrrole in the presence of a second monomer. In a further embodiment of the present disclosure, the process comprises polymerizing fluorinated dithienyl-diketopyrrolopyrrole in the presence of a second and a third monomer.

[0047] In an aspect, the present disclosure relates to a process for preparing fluorinated dithienyl-diketopyrrolopyrrole. In a further aspect, the present disclosure relates to a process for preparing fluorinated dithienyl-diketopyrrolopyrrole and derivatives thereof.

[0048] In an aspect, the present disclosure relates to a process for preparing pure 4- fluoro-2-thiophenecarbonitrile. In an embodiment, the present disclosure relates to a process for preparing pure 3,4-difluoro-2-thiophenecarbonitrile.

[0049] In an aspect, the present disclosure relates to a process for preparing 4-fluoro-2- thiophenecarbonitrile, the process comprising reacting a compound of formula I with an organolithium reagent and a fluorinating agent to obtain a compound of formula II wherein Ai, A 2 and A3 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl or cycloalkyl.

[0050] In an embodiment of the present disclosure, the compounds of formula I and II have the structures

respectively. [0051] In a particular embodiment of the present disclosure, the organolithium reagent is ft-BuLi. In a particular embodiment of the present disclosure, the fluorinating agent is reagent is NFSI. In a further particular embodiment of the present disclosure the NFSI is recrystallized prior to use. In a particular embodiment of the present disclosure, the process further comprises the use of TMED A. In a particular embodiment of the present disclosure, the reaction is carried out at -100°C.

[0052] In an aspect, the present disclosure relates to a process for preparing 4-fluoro-5- alkylsilyl-2-thiophenecarbonitrile, the process comprising reacting a compound of formula I with an organolithium reagent and a fluorinating agent to obtain a compound of formula II and reacting the compound of formula II with an organolithium reagent and a cyanating agent to obtain a compound of formula III wherein Ai, A 2 and A3 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl or cycloalkyl.

[0053] In an embodiment of the present disclosure, the compounds of formula I, II and III have the structures respectively.

[0054] In a particular embodiment of the present disclosure, the organolithium reagent is at least one of «-BuLi and t-BuLi. In a particular embodiment of the present disclosure, the fluorinating agent is reagent is NFSI. In a further particular embodiment of the present disclosure the NFSI is recrystallized prior to use. In a particular embodiment of the present disclosure, the cyanating agent is phenyl cyanate. In a particular embodiment of the present disclosure, the reaction is carried out at -80°C.

[0055] The foregoing and other advantages and features of the present disclosure will become more apparent upon reading of the following non-restrictive description of illustrative embodiments thereof, given by way of example only with reference to the accompanying drawings/figures.

BRIEF DESCRIPTION OF THE DRAWINGS/FIGURES

[0056] In the appended drawings/figures:

[0057] FIG. 1 illustrates the computationally calculated Gibbs free energy of the Concerted Metalation-Deprotonation (CMD) transition state associated with the transition state for C-H bond cleavage at the α, β and γ positions.

[0058] FIG. 2 illustrates the UV- Visible absorption spectra of polymers P3-P5 in solution in CHCb (left) and in the solid state (right).

[0059] FIG. 3 illustrates the transfer (left) and output (right) characteristics of a typical Bottom Gate Bottom Contact configuration (BGBC) OFET device with polymer P2 as the channel semiconductor, P2 showing ambipolar behavior. The P2 film was annealed at 100°C for 20 min under nitrogen.

[0060] FIG. 4 illustrates the current density- voltage (J-V) characteristics measured in the dark (full symbols) and under standard (AM1.5G 100 mW/cm 2 ) conditions (open symbols) for polymer P3 (squares), polymer P4 (triangles), polymer P5 with 1,8- diiodooctane (DIO; circles) and polymer P5 with diphenyl ether (DPE; diamonds).

[0061] FIG. 5 illustrates the external quantum efficiency measured for polymer P3 (squares), polymer P4 (triangles), polymer P5 with DIO (circles) and polymer P5 with DPE (diamonds).

[0062] FIG. 6 illustrates a wide angle X-ray scattering (WAXS) experiment for polymer P2.

[0063] FIG. 7 illustrates a wide angle X-ray scattering (WAXS) experiment for polymer P3.

[0064] FIG. 8 illustrates a wide angle X-ray scattering (WAXS) experiment for polymer P5.

[0065] FIG. 9 illustrates current- voltage curves of hole-only SCLC diodes for polymer P3 (triangles), polymer P4 (circles) and polymer P5 (squares). Dashed lines correspond to the expected JaV 2 dependence in the SCLC regime.

DETAILED DESCRIPTION

[0066] Glossary

[0067] In order to provide a clear and consistent understanding of the terms used in the present disclosure, a number of definitions are provided below. Moreover, unless defined otherwise, all technical and scientific terms as used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this specification pertains.

[0068] The word "a" or "an" when used in conjunction with the term "comprising" in the claims and/or the specification may mean "one", but it is also consistent with the meaning of "one or more", "at least one", and "one or more than one" unless the content clearly dictates otherwise. Similarly, the word "another" may mean at least a second or more unless the content clearly dictates otherwise.

[0069] As used in this specification and claim(s), the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "include" and "includes") or "containing" (and any form of containing, such as "contain" and "contains"), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.

[0070] As used in this specification and claim(s), the word "consisting" and its derivatives, are intended to be close ended terms that specify the presence of stated features, elements, components, groups, integers, and/or steps, and also exclude the presence of other unstated features, elements, components, groups, integers and/or steps.

[0071] The term "consisting essentially of, as used herein, is intended to specify the presence of the stated features, elements, components, groups, integers, and/or steps as well as those that do not materially affect the basic and novel characteristic(s) of these features, elements, components, groups, integers, and/or steps.

[0072] The terms "about", "substantially" and "approximately" as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±1% of the modified term if this deviation would not negate the meaning of the word it modifies.

[0073] The term "suitable" as used herein means that the selection of the particular compound or conditions would depend on the specific synthetic manipulation to be performed, and the identity of the molecule(s) to be transformed, but the selection would be well within the skill of a person trained in the art. All process/method steps described herein are to be conducted under conditions sufficient to provide the product shown. A person skilled in the art would understand that all reaction conditions, including, for example, reaction solvent, reaction time, reaction temperature, reaction pressure, reactant ratio and whether or not the reaction should be performed under an anhydrous or inert atmosphere, can be varied to optimize the yield of the desired product and it is within their skill to do so.

[0074] The expression "proceed to a sufficient extent" as used herein with reference to the reactions or process steps disclosed herein means that the reactions or process steps proceed to an extent that conversion of the starting material to product is maximized. Conversion may be maximized when greater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 99% of the starting material is converted to product.

[0075] The term "substituted" as used herein, means that a hydrogen radical of the designated moiety is replaced with the radical of a specified substituent, provided that the substitution results in a stable or chemically feasible compound. Non-limiting examples of substituents include halogen (F, CI, Br, or I) for example F, hydroxyl, thiol, alkylthiol, alkoxy, amino, amido, carboxyl, alkyl, cycloalkyl, arene, heteroarene and cyano.

[0076] As used herein, the term "alkyl" can be straight-chain or branched. This also applies if they carry substituents or occur as substituents on other residues, for example in alkoxy residues, alkoxycarbonyl residues or arylalkyl residues. Substituted alkyl residues can be substituted in any suitable position. Examples of alkyl residues containing from 1 to 25 carbon atoms are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, the ^-isomers of all these residues, isopropyl, isobutyl, isopentyl, neopentyl, isohexyl, isodecyl, 3-methylpentyl, 2,3,4-trimethylhexyl, sec-butyl, tert-butyl, or tert-pentyl. A specific group of alkyl residues is formed by the residues methyl, ethyl, ^-propyl, isopropyl, «-butyl, isobutyl, sec-butyl and tert-butyl.

[0077] As used herein, the term "lower alkyl" can be straight-chain or branched. This also applies if they carry substituents or occur as substituents on other residues, for example in alkoxy residues, alkoxycarbonyl residues or arylalkyl residues. Substituted alkyl residues can be substituted in any suitable position. Examples of lower alkyl residues containing from 1 to 10 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0078] As used herein, the term "cycloalkyl" is understood as being a carbon-based ring system, non-limiting examples of which include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0079] The terms "alkoxy" or "alkyloxy," as used interchangeably herein, represent an alkyl group attached to the parent molecular group through an oxygen atom.

[0080] The term "alkylsulfmyl" as used herein, represents an alkyl group attached to the parent molecular group through an S(O) group.

[0081] The term "alkylsulfonyl," as used herein, represents an alkyl group attached to the parent molecular group through a S(0) 2 group.

[0082] The term "alkylthio" as used herein, represents an alkyl group attached to the parent molecular group through a sulfur atom.

[0083] The term "alkenyl," as used herein, represents monovalent straight or branched chain groups of, unless otherwise specified, from 2 to 15 carbons, such as, for example, 2 to 6 carbon atoms or 2 to 4 carbon atoms, containing one or more carbon-carbon double bonds and is exemplified by ethenyl, 1-propenyl, 2-propenyl, 2-methyl-l-propenyl, 1-butenyl, 2- butenyl and the like and may be optionally substituted with one, or more substituents.

[0084] The term "alkynyl" as used herein, represents monovalent straight or branched chain groups of from 2 to 15 carbon atoms comprising a carbon-carbon triple bond and is exemplified by ethynyl, 1-propynyl, and the like and may be optionally substituted with one or more substituents.

[0085] The terms "carboxy" or "carboxyl," as used interchangeably herein, represents a C0 2 H group. [0086] The term "carbamate" as used herein refers to an ester group represented by the general structure -NH(CO)0-. Carbamate esters may have alkyl or aryl groups substituted on the nitrogen, or the amide function. The carbamate group can be secondary (NH) or tertiary (N).

[0087] As used herein, the term "arene" is understood as being an aromatic substituent which is a single ring or multiple rings fused together and which is optionally substituted. When formed of multiple rings, at least one of the constituent rings is aromatic. In an embodiment, arene substituents include phenyl, naphthyl, indane, and fluorene groups.

[0088] The term "heteroarene" as used herein embraces fully unsaturated or aromatic heterocyclo groups which are optionally substituted. The heteroarene groups are either monocyclic, bicyclic, tricyclic or quadracyclic, provided they have a suitable number of atoms, for example from 3 to 30 atoms, and are stable. A bicyclic, tricyclic or quadracyclic heteroaryl group is fused, bridged and/or simply linked via a single bond. Examples of heteroarene groups include unsaturated 3 to 6 membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, for example, pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazolyl (e.g., 4H-l ,2,4-triazolyl, 1H-1 ,2,3- triazolyl, 2H-l ,2,3-triazolyl, etc.), tetrazolyl (e.g. lH-tetrazolyl, 2H-tetrazolyl, etc.), etc.; unsaturated condensed heterocyclo groups containing 1 to 5 nitrogen, oxygen and/or sulfur atoms including, for example, indolyl, isoindolyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl, tetrazolopyridazinyl (e.g., tetrazolo[l ,5- b]pyridazinyl, etc.), etc.; unsaturated 3 to 6-membered heteromonocyclic groups containing an oxygen atom, including, for example, pyranyl, furyl, etc.; unsaturated 3 to 6-membered heteromonocyclic groups containing a sulfur or a selenium atom, including for example, thienyl, selenophen-yl, etc.; unsaturated 3- to 6-membered heteromonocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, including, for example, oxazolyl, isoxazolyl, oxadiazolyl (e.g., 1 ,2,4-oxadiazolyl, 1 ,3,4-oxadiazolyl, 1 ,2,5-oxadiazolyl, etc.) etc.; unsaturated condensed heterocyclo groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms (e.g. benzoxazolyl, benzoxadiazolyl, etc.); unsaturated 3 to 6-membered heteromonocyclic: groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms, including, for example, thiazolyl, thiadiazolyl (e.g., 1 ,2,4-thiadiazolyl, 1 ,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, etc.) etc.; unsaturated condensed heterocyclo groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms (e.g., benzothiazolyl, benzothiadiazolyl, etc.), unsaturated linked 5 or 6-membered heteromonocyclic groups containing 1 to 2 sulfur atoms and/or 1 to 3 nitrogen atoms, including, for example, bithienyl and trithienyl and the like. The term also embraces groups where heterocyclo groups are fused with aryl groups. Examples of such fused bicyclic groups include benzofuran, benzothiophene, benzopyran, and the like.

[0089] The term "derivative" as used herein, is understood as being a substance which comprises the same basic carbon skeleton and carbon functionality in its structure as a given compound, but can also bear one or more substituents or rings.

[0090] The term "analogue" as used herein, is understood as being a substance similar in structure to another compound but differing in some slight structural detail.

[0091] The term "ambipolar" layer or material as used herein means that the layer does not substantially block either electrons or holes when used as one layer in a multi-layer organic electronic device (e.g. an OFET). The material constituting the layer is capable of transferring both electrons and holes effectively. As a result, both electrons and holes can penetrate deep into the host layer, resulting in a broad recombination zone and a high quantum efficiency at low operating voltage.

[0092] The term "silane reagent" as used herein is represented by the formula SiA 1 A 2 A 3 X where A 1 , A 2 and A 3 can be, independently, hydrogen, or a substituted or unsubstituted alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl or cycloalkyl, and wherein X is a halogen.

[0093] The term "halogen" or "halo" as used interchangeably herein, represents F, CI, Br and I.

[0094] The term "direct heteroarylation" means that none of the monomers used in the heteroarylation process comprises a sacrificial organometallic functionality at the position of the coupling. Heteroarylation occurs when the monomers comprise at least one heteroaryl. Organometallic refers to compounds which have an organic group bonded to a metal or metalloid through a carbon-metal bond. A non-limiting example of an organometallic is an organotin compound such as frequently encountered in Stille Coupling reactions.

[0095] The term "under conditions for the direct heteroarylation" refers to the reaction conditions used to effect the coupling of heteroaryl monomers in the presence of one or more ligands and one or more catalysts. In an embodiment, these conditions comprise, consist of or consist essentially of the combining of the one or more monomers, ligands and catalysts under an inert atmosphere and optionally with an inert solvent, followed by heating. In an embodiment, the one or more monomers, ligands and catalysts and optional solvent are heated to a temperature of about 50°C to about 200°C, or about 100°C to about 150°C. In an embodiment an inert organic solvent is used to substantially dissolve the one or more monomers, ligands and catalysts. In a further embodiment, these conditions comprise, consist of or consist essentially of the combining of the one or more monomers, ligands and catalysts, optionally under an inert atmosphere, and optionally with an inert solvent, followed by heating.

[0096] The term "inert solvent" as used herein refers to any solvent or mixture of solvents in which the reagents in a chemical reaction are substantially soluble, at least to the extent to allow the chemical reaction, and which does not interfere with or inhibit the chemical reaction. The selection of a suitable inert solvent is well within the skill of a person in the art.

[0097] The expression "hydrogen that is activated for direct heteroarylation reactions" as used herein refers to hydrogen atoms on a heteroaryl group that, due to the specific structure or substitution patterns of the heteroaryl group, are reactive under direct heteroarylation conditions. By "reactive under direct heteroarylation conditions" it is meant to participate in the reaction with the catalyst(s) and ligand(s) to result in bond formation between the carbon to which the activated hydrogen is attached and a carbon to which an "X" group is attached on a second heteroaryl group. A hydrogen is activated, for example, by attaching an electron withdrawing group at a position alpha to the carbon atom containing the activated hydrogen. Non-limiting examples of electron withdrawing groups are carbonyl-containing functional groups (C(O)-R), cyano and nitro, wherein R is alkyl, cycloalkyl or O-alkyl. Alternatively, a heteroatom, such as N, O, S or Se may be located alpha to the carbon atom containing the activated hydrogen.

[0098] The term "substituted" as used herein, means that a hydrogen atom of the designated moiety is replaced with a specified substituent, provided that the substitution results in a stable or chemically feasible compound. Non-limiting examples of substituents include halogen (F, CI, Br, or I) for example Br, CN, C(0)-R and alkyl groups, wherein R is alkyl, cycloalkyl or O-alkyl.

[0099] The term "oligomer" as used herein, refers to a molecule comprising at least two repetitive units. In an embodiment of the present disclosure, the oligomer will comprise at least 3 or at least 4 or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10 repetitive units.

[00100] The term "polymer" as used herein generally includes, but is not limited to, homopolymers and copolymers, such as for example block, random and alternating copolymers.

[00101] Despite the similar size of both the fluorine and hydrogen atoms, the fluorination of the phenyl groups of diphenyl-DPP led to an undesired torsion of the resulting fluorinated diphenyl-DPP core.'- 7 -' While the alkylated diphenyl-DPP core is known to be twisted and the alkylated dithienyl-DPP core is known to be coplanar, it was surmised that fluorinating the thiophene moieties of dithienyl-DPP could possibly also adversely affect the coplanarity of the resulting fluorinated dithienyl-DPP core which in turn could have an adverse effect on the electro -optical properties. To gauge the effect of both the number and position of the fluorine atoms on the molecular structure of the fDT- DPP monomers, density functional conformational analyses were performed (Table 1). [00102] Table 1: Calculated energies and torsion angles of the syn- and a«t -conformers of various DPP monomers.

[00103] The analyses revealed that when the fluorine atom is pointing towards the DPP core (DPP-3-F), the coplanarity is lost. However, when the fluorine atom is pointing away from the DPP core (DPP-4-F), the coplanarity is maintained. The syn- and a«t -conformers are illustrated in Scheme 1.

Scheme 1

[00104] The effect of both the number and position of the fluorine atoms on the activation energy (Gibbs free energy) of the C-H bond of the thiophene moiety of the fDT- DPP monomers in a catalytic direct heteroarylation polymerization reaction was analyzed. As shown in FIG. 1 with reference to DPP, a difference in the activation energy (AE a ) of 4.8 kcal mol "1 was calculated between H a (24.2 kcal mol "1 ) and Hp (29.0 kcal mol "1 ), resulting in a selectivity ratio of about 450/1 favoring H a . On the other hand, a difference in the activation energy (AE a ) of 10.3 kcal mol "1 was calculated between H a (24.2 kcal mol " l ) and Η γ (34.5 kcal mol "1 ) resulting in a selectivity ratio of about 530000/1 favoring H a . With reference to DPP-3,4-F, only one C-H bond is available for the concerted metalation- deprotonation (CMD) step in the direct heteroarylation polymerization (DHAP) reaction with an activation energy calculated at 19.4 kcal mol "1 . This lower activation energy, when compared to the activation energy of H a of DPP (24.2 kcal mol "1 ) illustrates the effect of electron withdrawing fluorine atoms on the C-H bond. With reference to DPP-3-F, a difference in the activation energy (ΔΕ α ) of 2.0 kcal mol "1 was calculated between H a (23.5 kcal mol "1 ) and Hp (25.5 kcal mol "1 ). The electron-withdrawing fluorine atom strongly modifies the activation energy of the C-Hp bond (25.5 kcal mol "1 while only having a minor impact on the activation energy of the C-H a bond (23.5 kcal mol "1 ). Indeed, while the activation energy of the C-H a bond (23.5 kcal mol "1 ) is only slightly lowered relative to the C-Ha bond of DPP (24.2 kcal mol "1 ), the activation energy of the C-Hp bond (25.5 kcal mol "1) is lowered more significantly relative to the C-Hp bond (29.0 kcal mol "1) of DPP, resulting in a selectivity ratio of only about 15/1 favoring H a for DPP-3-F as compared to the selectivity ratio of about 450/1 favoring H a for DPP. Finally, with reference to DPP-4- F, a difference in the activation energy (ΔΕ α ) of 10.3 kcal mol "1 was calculated between H a (19.8 kcal mol "1 ) and Η γ (30.1 kcal mol "1 ). The electron-withdrawing fluorine atom thus influences the activation energy of both the C-H a and C-H Y bonds. Indeed, the activation energy of the C-H a bond (19.8 kcal mol "1 ) is lowered relative to the C-H a bond of DPP (24.2 kcal mol "1 ) while the activation energy of the C-H Y bond (30.1 kcal mol "1 ) is lowered relative to the C-H Y bond of DPP (34.5 kcal mol "1 ). Notwithstanding the activation energy lowering effect of the fluorine atom on both the C-H a and C-H Y bonds, the difference in the activation energy (ΔΕ α ) of 10.3 kcal mol "1 results in a selectivity ratio of 531000/1 favoring Ha over Η γ . The polymerization of the DPP-4-F core and derivatives thereof by DHAP, will thus likely proceed at the a-position, leading to coplanar and well-defined polymer or co-polymer.

[00105] In an embodiment, the present disclosure relates to a process for preparing pure 4-fluoro-2-thiophenecarbonitrile (6). In a further embodiment, the present disclosure relates to a process for preparing pure 3,4-difluoro-2-thiophenecarbonitrile. A general synthetic route for preparing 4-fluoro-2-thiophenecarbonitrile (6), in accordance with an embodiment of the present disclosure, is depicted in Scheme 2.

Organolithium Reagent

Ligand

Fluorinating Agent

Solvent

Desilylating Agent

Solvent

6

Scheme 2

[00106] Various reagents and conditions appropriate for conversion of the aldehyde function into the desired nitrile (*) are known to the skilled person. Moreover, a person skilled in the art would understand that all reaction conditions, including, for example, reaction solvent, reaction time, reaction temperature, reaction pressure, reactant ratio and whether or not the reaction should be performed under an anhydrous or inert atmosphere, can be varied to optimize the yield of the desired product and it is within their skill to do so. An inert atmosphere includes, for example, under nitrogen or argon. Heating temperatures will vary depending on the reactants, however, will generally be about 50°C to about 200°C, or about 100°C to about 150°C. Reaction times will also vary depending on the reactants, but can be determined using methods known in the art, for example, by following the reaction progress by thin layer chromatography (TLC) or nuclear magnetic resonance (NMR) spectroscopy, and monitoring the disappearance of starting materials and/or formation of product. Reactions will be complete when a sufficient amount of the product is formed. Reaction solvents, temperatures and times are parameters that are readily selected by a person of skill in the art.

[00107] An exemplary synthetic route for preparing 4-fluoro-2-thiophenecarbonitrile (6), in accordance with an embodiment of the present disclosure, is depicted in Scheme 3. n-Bul

D MI_

Scheme 3

[00108] 3-Bromo-2-(dimethyloctylsilyl)-thiophene (2) was prepared by the lithiation of 2,3-dibromothiophene (1) with «-BuLi in diethyl ether at -80°C, followed by treatment with ft-octyldimethylchlorosilane. The crude product was subsequently purified by vacuum distillation affording the desired 3-bromo-2-(dimethyloctylsilyl)-thiophene as a colorless oil in 85% yield. The lithiation of 2 with «-BuLi and TMEDA in THF at -100°C, followed by the addition of freshly recrystallized N-fluorobenzenesulfonimide (NFSI) via cannula, provided the desired 3-fluoro-2-(dimethyloctylsilyl)-thiophene (3) product in 65% yield. The fluorination reaction also produced traces of dehalogenated 2-(dimethyloctylsilyl)- thiophene product which could be readily removed by normal phase chromatography. The subsequent lithiation of 3 with «-BuLi in THF at -80°C, followed by quenching of the reaction mixture with N^-dimethylformamide (DMF), afforded the 4-fluoro-5- (dimethyloctylsilyl)-2-thiophenecarboxaldehyde (4) product in 85% yield. The subsequent treatment of 4 with an excess of tetrabutylammonium fluoride trihydrate (TBAF.3H 2 0) in a mixture of THF/HCI at room temperature, afforded the 4-fluoro-2- thiophenecarboxaldehyde (5) product in 85% yield. The subsequent treatment of 5 with hydroxylamine hydrochloride (NH 2 OH.HCl) in NMP at 145°C, followed by purification by column chromatography, afforded the 4-fluoro-2-thiophenecarbonitrile (6) product in 80% yield without any traces of 2-thiophenecarbonitrile. The purity of the 4-fluoro-2- thiophenecarbonitrile (6) product is of critical importance for the next steps leading to the formation of the fluoro-dithienyl-DPP (fDT-DPP) core (Scheme 4). [00109] In an aspect of the present disclosure, 4-fluoro-2-thiophenecarbonitrile (6) and 3,4-difluoro-2-thiophenecarbonitrile are used as building blocks for the preparation of novel fluoro-dithienyl-DPP (fDT-DPP) monomers. An exemplary synthetic route for the preparation of novel fDT-DPP monomers using 4-fluoro-2-thiophenecarbonitrile (6), in accordance with an embodiment of the present disclosure, is depicted in Scheme 4. The synthesis of the fDT-DPP monomers proceeded smoothly following a succinate-based procedure.

Scheme 4

[00110] 3,6-(4-Fluorothiophen-2-yl)pyrrolo[3,4-c]pyrrole-l,4-dione (7) was prepared in one step by the consecutive condensation of succinate ester with 4-fluoro-2- thiophenecarbonitrile (6) in the presence of sodium alkoxide in 75% yield. In addition to modifying the electronic properties of the DT-DPP core, the fluorine atoms also prevent β- branching and activate the C-H a bond toward DHAP. Alkylation of 7 with either 1- bromodecane or 1-bromododecane afforded M5 or M6 in 40% and 43% yield, respectively.

[00111] A further exemplary synthetic route for preparing 4-fluoro-2- thiophenecarbonitrile (6), and its subsequent use in the preparation of 3,6-(4- fluorothiophen-2-yl)pyrrolo[3,4-c]pyrrole-l,4-dione (7), in accordance with an embodiment of the present disclosure, is depicted in Scheme 5.

Scheme 5

[00112] A further exemplary synthetic route for preparing 3,6-(4-fluorothiophen-2- yl)pyrrolo[3,4-c]pyrrole-l,4-dione (7), in accordance with an embodiment of the present disclosure, is depicted in Scheme 6.

Scheme 6

[00113] In an aspect, the present disclosure relates to a method for preparing a polymer comprising treating one or more monomers, one or more catalysts and one or more ligands under conditions for the direct heteroarylation of the at least one or more monomers to provide the polymer; and isolating the polymer. In an embodiment, the present disclosure relates to a method for preparing a polymer comprising treating fDT-DPP in the presence of a second monomer, one or more catalysts and one or more ligands under conditions for the direct heteroarylation of the fDT-DPP to provide the polymer; and isolating the polymer.

[00114] In an embodiment, the present disclosure relates to a method for preparing a polymer comprising treating one or more alkylated fDT-DPP monomers, one or more catalysts and one or more ligands under conditions for the direct heteroarylation of the at least one or more alkylated fDT-DPP monomers to provide the polymer; and isolating the polymer. Exemplary alkylated fDT-DPP monomers are depicted in Scheme 7.

Scheme 7

[00115] In an aspect of the present disclosure, the alkylated fDT-DPP building blocks (monomers) are polymerized by direct heteroarylation polymerization (DHAP). Exemplary copolymers obtained by DHAP, in accordance with various embodiments of the present disclosure, are depicted in Scheme 8.

Scheme 8

[00116] PI was prepared as previously reported in the literature. [ ] P2-P5 were prepared by direct heteroarylation polymerization. In all cases, the polymerization reaction was stopped upon gelation of the reaction mixture. Following precipitation in methanol, the polymers were purified by successive Soxhlet extractions. Surprisingly, the presence of the fluorine atoms on the fDT-DPP core led to shorter polymerization times and higher molecular weights relative to their non-fluorinated analogues (Table 2). Indeed, P3 exhibits a number-average molecular weight of 44 kg mol "1 following a polymerization period of 16 hours, whereas P4 exhibits a number-average molecular weight of 51 kg mol "1 after only 30 min of polymerization time. Moreover, the size of the phosphine-based ligand was also shown to have a direct impact on the selectivity of the DHAP reaction while decreasing the incidence of homocoupling. [ ] When P5 was prepared using tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) instead of tris(2-methoxyphenyl)phosphine, a number-average molecular weight of 125 kg mol "1 was obtained after only 30 min of polymerization time.

[00117] Table 2: Selected physical, optical and electrical properties of polymers P1-P5.

[00118] Table 3: Selected physical, optical and electrical properties of polymers P7-P15.

afrom CV measurements; ¾ΙΜΟ = E G + EHOMO

[00119] The thermal properties of the fDT-DPP-based polymers and copolymers were evaluated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). All polymers were shown to exhibit good thermal stability with only a 5% weight loss at temperatures higher than 400°C, while DSC traces did not reveal any thermal transition.

[00120] The fDT-DPP-based polymers and copolymers exhibited broad and red shifted absorption in the UV-vis-NIR region with deeper HOMO energy levels as compared to their non-fluorinated analogues. The solid-state UV-Vis-NIR absorption spectrum of PI shows a maximum of absorption at 927 nm with a shoulder at 846 nm, and an optical bandgap of 1.17 eV. Bathochromic shifts were observed for P2, for both the maximum of absorption (40 nm) and the shoulder (13 nm), relative to PI. An optical bandgap of 1.15 eV was determined for P2. An effect of the fluorine atom on the optical properties was also observed for P4 and P5 in dilute chloroform solution (FIG. 2). Indeed, a strong bathochromic shift (47 nm) of the maximum of absorption was observed for P4 and P5 (702 nm) relative to P3 (655 nm). However, in the solid state, a bathochromic shift (34 nm) of the maximum of absorption was observed for P3 (relative to P3 in solution) while no such behavior was observed for either P4 or P5, suggesting strong aggregation in solution for the latter polymers. X-Ray diffraction analyses (powder) were also performed on P2, P3 and P5 (FIGs. 6-8). D-Spacing and lamellar distances typical for conjugated polymers were found for each of the fDT-DPP copolymers.

[00121] Additional fDT-DPP-based polymers and copolymers in accordance with various embodiments of the present disclosure, are depicted in Scheme 9. In a further embodiment of the present disclosure, the fDT-DPP-based polymers and copolymers are obtained by direct heteroarylation polymerization (DHAP).

Scheme 9

[00122] In an aspect of the present disclosure, the fDT-DPP-based polymers and copolymers are used in the manufacture of organic electronics devices. In an embodiment of the present disclosure, the fDT-DPP-based polymers and copolymers are used in PSCs and OFETs. In a further embodiment of the present disclosure, the fDT-DPP-based polymers and copolymers are used in the manufacture of single-semiconductor complementary metal-oxide-semiconductor (CMOS) inverters and light emitting devices. Without being bound by theory, it is believed that fDT-DPP is capable of inducing ambipolarity in OFETs making them specifically attractive for the fabrication of single- semiconductor complementary metal-oxide-semiconductor (CMOS) inverters and light emitting devices. Indeed, a single organic semiconductor would facilitate the fabrication of CMOS-inverters while also making the devices more stable in comparison to the semiconductor blends and/or double-layer semiconductor films which have been shown to be subject to nanomorphological changes in the blended films or coalescing of the bilayers.^ Even though ambipolar polymers, based on naphthalene diimide (NDI), benzodifurandione (BDF), isoindigo (IID) or diketopyrrolopyrrole (DPP) or its derivatives as electron acceptors have been previously reported, only a small number of polymeric semiconductors displaying ambipolar characteristics with both high and balanced hole and electron mobilities are known '19 ^ It is surmised that fDT-DPPs could lead to more efficient PSCs owing to the stabilization of the HOMO energy levels, which often contributes to the enhancement of the open-circuit voltage. In an embodiment of the present disclosure, fluorinated dithienyl-DPP (fDT-DPP) pseudo-homopolymer (P2) was synthesized for OFETs applications while fluorinated-DPP/carbazole copolymers (P3-P5) were synthesized for PSCs applications.

[00123] In an aspect of the present disclosure, the alkylated fDT-DPP building blocks (monomers) are polymerized by Stille polymerization. Exemplary polymers and copolymers obtained by Stille polymerization are depicted in Scheme 10.

Scheme 10 [00124] Fabrication and Testing of OFETs

[00125] Organic field effect transistors (OFETs) were fabricated on a heavily n ++ -doped Si/Si0 2 substrate having a bottom-gate bottom-contact configuration (BGBC). The thermally grown Si0 2 (-300 nm) was used as the gate dielectric and the conductive Si layer functioned as the gate. The gold source/drain contact pairs, with a channel length of 30 μιη and a channel width of 1000 μιη, were obtained by conventional photolithography and thermal deposition. The substrate was then plasma treated, cleaned by ultra-sonication with acetone and isopropanol, dried with nitrogen and baked at 120°C for 1 min. The substrate was then cooled to room temperature, dried, and submerged in a dodecyltrichlorosilane (DDTS) solution (3% in toluene) for 20 min followed by rinsing with toluene and drying with nitrogen. A polymer layer was subsequently deposited by spin-coating a polymer solution in o-dichlorobenzene (o-DCB) (10 mg mL "1 ) at 3000 rpm for 80 s in a glove box. After annealing at a pre-determined temperature in the glove box filled with nitrogen for 20 min, the devices were characterized (in the same glove box) using an Agilent B2912A Semiconductor Analyzer. The field-effect mobility in the saturation region was calculated according to the following equation:

W where IDS is the drain current, W and L are the device channel width and length, d is the gate dielectric layer capacitance per unit area (~1 1.6 nF cm -2 ), μ is the carrier mobility, and VGS and VTH are the gate voltage and threshold voltage.

[00126] In an embodiment of the present disclosure, the semiconducting properties of P2 were evaluated in bottom-gate/bottom-contact (BGBC) OFETs devices. All spin- coating processes were carried out under nitrogen, and the active channel layers were annealed at different temperatures for 20 min under nitrogen prior to measurements. The OFET characteristics of the devices were measured under nitrogen, and the field-effect mobility was extracted from the saturation regimes. P2 displayed ambipolar properties. The performance data of an OFET device manufactured in accordance with an embodiment of the present disclosure are illustrated in Table 4. Comparative data obtained for PI are also presented in Table 4. The transfer (left) and output (right) characteristics of the BGBC OFET device, with polymer P2 as the channel semiconductor, are illustrated in FIG. 3. The output characteristics follow a typical trend exhibited by ambipolar devices where a super-linear increase in current is observed at low VGS and high VDS, which is due to the injection of the opposite charge carrier, and a superposed standard saturation behavior with increasing VGS for the dominate charge carrier. From the transfer characteristics, V-shaped IDS patterns were observed. P2 exhibited high mobilities as illustrated by the μ- and μ Β maxima of 0.80 cm 2 V -1 s -1 and 0.51 cm 2 V -1 s -1 respectively (Table 4). The hole and electron mobilities are quite balanced with an average μβ/μΐι of 0.68. In all cases, forward and backward scans in the transfer and output curves exhibited pronounced hysteresis in drain-source current (IDS), which is frequently observed for OFETs due to trapping of the charge carriers in the gate dielectrics, at the interface of the active channel layer and dielectric, or in the active channel layer.

[00127] Table 4: OFET Performance.

"Maximum mobilities measured under nitrogen in saturated regime. The average values are in brackets. b Current on/off ratio. Calculated from the average mobilities. d Bottom Gate Bottom Contact configuration (BGBC), where the P2 films were annealed at 100°C for 20 min under nitrogen. e Top Gate Bottom Contact configuration (TGBC).

[00128] Fabrication and testing of Hole-Only Space Charge Limited Current (SCLC) Devices

[00129] ITO coated glass slides were used as substrates. The substrates were cleaned in an ultrasonic bath at 45°C for 15 min using consecutively soapsuds, acetone, and isopropanol, followed by a 15 min UV-ozone treatment. A thin poly(ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) layer was spin-coated onto the pre-cleaned ITO slides which were used as the bottom electrode. Polymer and polymer: fullerene layers were subsequently spin-coated from hot solutions (~1 10°C) onto pre-heated substrates (~1 10°C). The resulting devices were left overnight under high vacuum (~5xl 0 "7 mbar) followed by the deposition of a M0O3 (7 nm)/Ag (120 nm) layer by thermal evaporation. The SCLC diode (surface area: 1 mm 2 ) current-voltage characteristics were subsequently measured using a Keithley 4200 semiconductor characterization system.

[00130] Fabrication and testing of polymer solar cells (PSCs)

[00131] ITO coated glass slides were utilized as substrates. A ZnO layer (-20-25 nm) was spin-coated from a ZnO nanoparticle solution (Nanograde N10) onto pre-cleaned ITO slides, thermally annealed at 100°C for 10 min and used as an electron extracting electrode. Active layers were elaborated from o-DCB and o-DCB/additive (DIO/DPE) solutions, using blends of polymers and PC71BM as electron acceptor materials at various weight ratios. The concentration of the solutions was 8 mg/mL with respect to polymer content. A top electrode consisting of M0O3 (7 nm)/Ag (120 nm) was subsequently deposited by thermal evaporation under vacuum (~5xl 0 "7 mbar vacuum). Four diodes having a 12 mm 2 active area were subsequently elaborated per substrate. All characterization was performed under a nitrogen atmosphere in the dark with simulated AM1.5G standard irradiation (100 mW/cm 2 , Lot Oriel Sun 3000 solar simulator).

[00132] DPP-carbazole copolymers were previously investigated as electron donors in bulk heterojunction solar cells. As shown in FIG. 9, out-of-plan hole mobilities were measured for P3, P4 and P5 by using hole-only space-charge limited current (SCLC) devices (e.g. diodes). For pure polymer films, the hole mobilities were found to be slightly higher in the fluorinated polymers with values of (1.9±0.3) x 10 "4 and (2.3±0.4) x 10 "4 cm 2 V "1 s "1 for P4 and P5, respectively, relative to (5.0±1.0) x 10 "5 cm 2 V "1 s "1 as measured for P3. The hole mobilities observed for P4 and P5 make them interesting candidates as electron-donors in BHJ solar cells. In an embodiment of the present disclosure, P3-P5 were characterized in blends with [6,6]-phenyl-C7i-butyric acid methyl ester (PC70BM) as electron-acceptors using an inverted device structure. The current density- voltage (J-V) characteristics of the solar cells, measured under simulated AM 1.5G irradiation (100 mW/cm 2 ), are illustrated in FIG. 4. The PSC parameters are summarized in Table 5.

[00133] Table 5: Photovoltaic parameters measured with different polymers.

(Values in brackets are Average PCE values)

[00134] For both fluorinated polymers P4 and P5, using DIO as additive, the open- circuit voltage (Voc) is slightly higher (by roughly 38-47 mV) than for the non-fluorinated polymer P3, which is in good agreement with the experimental HOMO energy levels reported in Table 2. The PCEs for the fluorinated polymers P4 and P5 are higher than those obtained for the non-fluorinated analogue P3. Indeed, the best results are obtained for the high molecular weight polymer P5, with significantly larger short-circuit current densities (J sc ) and fill factors (FF). The average external quantum efficiencies (EQE), measured on the best-performing devices (FIG. 5), followed a similar trend. The J sc values estimated from the EQE spectra are in-line with those measured under AM 1.5 illumination. The noticeable difference in FF between non-fluorinated (P3) and fluorinated polymers (P4 and P5) correlates well with the higher out-of-plane mobility of P4 and P5, which allows for improved charge collection. Interestingly, the polymer molecular weight turns out to have a dramatic impact on the solar cell performance, despite its minor influence on the SCLC mobility. The increase in PCE is mostly due to the higher J sc of the P5-based devices and to a slightly larger FF. This in turn suggests that the molecular weight mostly affects the polymer/fullerene interface, at which charge generation occurs. The further enhancement in PCE, as observed when using a different additive (DPE versus DIO), supports this conclusion as the former is expected to influence principally the blend morphology by acting as a theta solvent. The PCE of 7.4% is among the highest values reported so far for conjugated polymers prepared by direct heteroarylation polymerization.

[00135] Table 6: Hole mobility (μ Η ) via OFETs (BG/BC) for P7-P9, Pll and P12.

*annealing at 130°C

[00136] Table 7: Electron Mobility (μ 6- ) via OFETs (BG/BC) for P8, P9, Pll and P12.

*annealing at 130°C

[00137] Table 8: Hole and Electron Mobility via SCLC for P7 and P12. [00138] Table 9: Solar Cell Performances for P7 and P10.

Mask: 9.00mm 2 , Light Intensity=100 mW/cm 2

[00139] EXPERIMENTAL

[00140] General: ¾ 13 C and 19 F NMR spectra were recorded on a Varian AS400 or Agilent DD2 500MHz spectrometer in deuterated solvents. Chemical shifts (δ) are reported in parts per million (ppm) relative to the residual protic solvent. The number- average ( n ) and weight-average ( w ) molecular weights were determined by size exclusion chromatography (SEC) using a Malvern HT-GPC system equipped with a refractive index (RI) detector. The flow rate was fixed at 0.75 mL/min using 1,2,4- trichlorobenzene (TCB) (with 0.0125% butylated hydroxytoluene (BHT) w/v) as eluent. The temperature of the system was set to 140°C. All the samples were prepared at concentrations of nominally 0.50 mg/mL in TCB. The sample vials were kept at 140°C with stirring for 1 h for complete dissolution. The calibration method used to generate the reported data was the classical polystyrene method using polystyrene narrow standards which were dissolved in TCB. UV-Vis absorption spectra were recorded using a Thermo Scientific Genesys 10S spectrophotometer using 1 cm path-length quartz cells. For solid- state measurements, polymer solutions was spun-cast on glass plates. Optical bandgaps were calculated from the onset of the absorption band. Cyclic voltammograms (CV) were recorded on a Solartron 1287 potentiostat using platinum wires as the working electrode and counter-electrode, at a scan rate of 50 mV/s, and a Ag/Ag + reference electrode (0.01 M of AgN0 3 in acetonitrile) in an anhydrous and argon-saturated solution of 0.1 M of tetrabutylammonium hexafluorophosphate (Bu4NPF 6 ) in acetonitrile (electrolyte). Under these conditions, the oxidation potential (E ox ) of ferrocene was 0.09V versus Ag/Ag + , whereas the E ox of ferrocene was 0.41 V versus saturated calomel electrode (SCE). The HOMO and LUMO energy levels were determined from the oxidation and reduction onsets from the CV spectra assuming the SCE electrode to be -4.7 eV from vacuum. Thermogravimetric analysis (TGA) measurements were carried out using a Mettler Toledo TGA SDTA 85 le apparatus at a heating rate of 10°C/min under a nitrogen atmosphere. The temperature of degradation (Td) corresponds to a 5% weight loss. Differential scanning calorimetric (DSC) analyses was performed using a Perkin-Elmer DSC-7 instrument, calibrated with ultra-pure indium at a scanning rate of 10°C/min under a nitrogen atmosphere. Wide-angle X-ray scattering (WAXS) diffraction (powder) measurements were performed using a Kristalloflex X-ray generator K760 (40kV, 40mA) equipped with a goniometer and a two-dimensional Hi-Star detector. The X-rays were produced using a sealed X-ray tube with a nickel filter emitting at 1.5418 A (Cu Ka). Diffractograms were acquired using control software (GADDS— General Area Detector Diffraction System).

[00141] Materials: 2,3-Dibromothiophene (1) was purchased from Combi-Blocks and n-octyldimethylchlorosilane was purchased from Gelest. N-Fluorobenzenesulfonimide (NFSI) was recrystallized in diethyl ether prior to use. PI, 2,7-Dibromo-9-(heptadecan-9- yl)-9H-carbazole (Ml), 3,6-Bis(thiophen-2-yl)-2,5-bis(decyl)pyrrolo[3,4-c]pyrrole-l ,4- dione (M2), 3,6-Bis(thiophen-2-yl)-2,5-bis(dodecyl)pyrrolo[3,4-c]pyrrole -l,4-dione (M3), 3,6-Bis(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo [3,4-c]pyrrole-l,4)-dione (M4), and tris(2-cycloheptyloxyphenyl)phosphine (BuraPhos) were synthesized according to reported literature procedures 20"24 ^

[00142] A number of non-limiting examples are provided in the following sections, illustrating the preparation of selected monomers and polymers in accordance with various embodiments of the present disclosure. The following non-limiting examples are illustrative of the present disclosure. [00143] Synthesis of 3-bromo-2-( dimethyloctylsilvD-thiophene (2)

[00144] Compound 1 (12.33g, 50.96 mmol, 1 eq.) was placed in a dried round-bottom flask with a magnetic stirrer and purged on a Schlenk line. Anhydrous diethyl ether (100 ml) was added and the solution was cooled to -80°C using an Et 2 0/N 2 ice bath. A solution of ft-BuLi (2.5 M in hexanes, 20.4 mL, 50.96 mmol, 1 eq.) was then added dropwise and the resulting mixture was left to react for 20 min at -80°C. Chlorodimethyloctylsilane (13.5 mL, 56.05 mmol, 1.1 eq.) was then rapidly added and the resulting reaction mixture was allowed to warm to room temperature and reacted overnight. The reaction was subsequently quenched with a saturated solution of NH4CI and extracted three times with diethyl ether. The combined organic phases were washed with water and brine, dried over MgS0 4 and concentrated under vacuum. Purification was achieved by vacuum distillation (b.p. 110-115°C at 0.35 mmHg) affording the title compound as a colorless oil (Y = 85%). ¾ NMR 500 MHz (CDCb) δ (ppm): 7.45 (d, J = 4.8 Hz, 1H), 7.10 (d, J = 4.8 Hz, 1H), 1.34-1.25 (m, 12H), 0.91-0.86 (m, 5H), 0.38 (s, 6H). 13 C NMR 126 MHz (CDCb) δ (ppm): 133.9, 132.6, 130.8, 117.4, 33.5, 32.1, 29.4, 23.8, 22.8, 15.5, 14.3, -2.3.

[00145] Synthesis of 3-fluoro-2-( dimethyloctylsilvD-thiophene (3)

[00146] 3-Bromo-2-(dimethyloctylsilyl)-thiophene (2) (5.64 g, 16.9 mmol, leq.) and tetramethylethylenediamine (TMEDA) (2.8 mL, 1.1 eq.) were placed in a dried round- bottom flask with a magnetic stirrer. The flask was subsequently purged on a Schlenk line. Anhydrous THF (180 ml) was added and the resulting solution cooled to -100°C using an Et 2 0/N2 bath. Freshly recrystallized N-Fluorobenzenesulfonimide (NFSI) (6.4 g, 20.3 mmol, 1.2 eq.) was solubilized in anhydrous THF (60 mL) in second round-bottom flask under argon and also cooled to -100°C. n- uhi (2.5 M in hexane, 2.8 mL, 17.75 mmol, 1.05 eq.) was then added dropwise into the solution of 2, which was left to react for 25 minutes at -100°C. The solution with NFSI was then rapidly added dropwise to the organolithium mixture via a cannula while maintaining the temperature of both flasks at - 100°C. The resulting reaction mixture was then allowed to warm to room temperature and was left to react overnight. The reaction mixture was subsequently quenched with a saturated solution of NH4CI and extracted three times with hexanes. The combined organic phases were washed with water and brine, dried over MgS0 4 and concentrated under vacuum. Purification was achieved by silica gel column chromatography using hexanes as eluent affording the title compound as a colorless oil (Y = 65%). ¾ NMR 500 MHz (Acetone-i e) δ (ppm): 7.66 (dd, J = 5.0 Hz, 2.9 Hz, 1H), 6.95 (dd, J= 5.0 Hz, 1.5 Hz, 1H), 1.40-1.27 (m, 12H), 0.87 (t, j = 7.0 Hz, 3H), 0.83-0.80 (m, 2H), 0.31 (s, 6H). 19 F NMR 470 MHz (Acetone-i e) δ (ppm): -122.4. 13 C NMR 101 MHz (CDCb) δ (ppm): 163.7 (d, J = 255.4 Hz), 129.8 (d, J = 8.6 Hz), 118.2 (d, J = 31.3 Hz), 114.4 (d, J = 30.9), 33.5, 32.1, 29.4, 23.8, 22.8, 16.2, 14.3, -2.1.

[00147] Synthesis of 3-fluoro-2-(dimethyloctylsilyl)-thiophene (3)

[00148] 3-Bromo-2-(dimethyloctylsilyl)-thiophene (2) (4.45 g, 13.36 mmol, leq.) was placed in a dried round-bottom flask with a magnetic stirrer. The flask was subsequently purged on a Schlenk line. Anhydrous diethyl ether (45 ml) was added and the resulting solution cooled to -80°C. Freshly recrystallized N-Fluorobenzenesulfonimide (NFSI) (5.05 g, 16.03 mmol, 1.2 eq.) was solubilized in anhydrous THF (100 mL) in second round- bottom flask under argon and also cooled to -80°C. t-BuLi (1.7 M in pentane, 9.4 mL, 16.03 mmol, 1.2 eq.) was then added dropwise into the solution of 2, which was left to react for 30 minutes at -80°C. The organolithium solution was then rapidly added dropwise to the NFSI solution via a cannula while maintaining the temperature of both flasks at - 80°C. The resulting reaction mixture was then allowed to warm to room temperature and was left to react overnight. The reaction mixture was subsequently quenched with a saturated solution of NH 4 C1 and extracted three times with hexanes. The combined organic phases were washed with water and brine, dried over MgS0 4 and concentrated under vacuum. Purification was achieved by silica gel column chromatography using hexanes as eluent affording the title compound as a colorless oil (Y = 85%). ¾ NMR 500 MHz (Acetone-i e) δ (ppm): 7.66 (dd, J = 5.0 Hz, 2.9 Hz, 1H), 6.95 (dd, J= 5.0 Hz, 1.5 Hz, 1H), 1.40-1.27 (m, 12H), 0.87 (t, j = 7.0 Hz, 3H), 0.83-0.80 (m, 2H), 0.31 (s, 6H). 19 F NMR 470 MHz (Acetone-i e) δ (ppm): -122.4. 13 C NMR 101 MHz (CDCb) δ (ppm): 163.7 (d, j = 255.4 Hz), 129.8 (d, J = 8.6 Hz), 118.2 (d, J = 31.3 Hz), 114.4 (d, J = 30.9), 33.5, 32.1, 29.4, 23.8, 22.8, 16.2, 14.3, -2.1.

[00149] Synthesis of 4-fluoro-5-( dimethyloctylsilyl)-2-thiophenecarboxaldehyde (4)

[00150] 3-Fluoro-2-(dimethyloctylsilyl)-thiophene (3) (1.45g, 5.31 mmol, 1 eq.) was placed in a dried round-bottom flask with a magnetic stirrer and purged on a Schlenk line. Anhydrous THF (20 ml) was added and the solution was cooled to -78°C. A solution of n- BuLi (2.5 M in hexanes, 2.35 mL, 5.84 mmol, 1.1 eq.) was then added dropwise and the mixture was reacted for 20 min at -78°C. Anhydrous DMF (0.9 mL, 10.6 mmol, 2 eq.) was subsequently added and the reaction mixture was allowed to warm to room temperature and left to react overnight. The reaction mixture was quenched with a saturated solution of NH4CI and extracted three times with diethyl ether. The combined organic phases were washed with water and brine, dried over MgS0 4 and concentrated under vacuum. Purification was achieved by silica gel column chromatography (eluent: ethyl acetate/hexanes 10/90) affording the title compound as a colorless oil (Y = 80%). 1 H NMR 500 MHz (CDCb) δ (ppm): 9.80 (d, J = 0.4 Hz, 1H), 7.46 (d, J = 1.8 Hz, 1H), 1.34-1.24 (m, 12H), 0.87 (t, J = 7.0 Hz), 0.83-0.80 (m, 2H), 0.35 (d, J = 0.35 Hz 6H). 19 F NMR 470 MHz (CDCb) δ (ppm): -116.6. 13 C NMR 101 MHz (CDCb) δ (ppm): 181.7 (d, J = 2.0 Hz), 162.9 (d, J = 258.4 Hz), 144.9 (d, J = 4.7 Hz), 127.8 (d, J = 30.8 Hz), 124.4 (d, J = 28.7 Hz), 33.4, 32, 29.3, 23.6, 22.8, 15.7, -2.4.

[00151] Synthesis of 4-fluoro-2-thiophenecarboxaldehyde (5)

[00152] 4-Fluoro-5-(dimethyloctylsilyl)-2-thiophenecarboxaldehyde (4) (0.6 g, 1.99 mmol, 1 eq.) was placed in a round-bottom flask with a magnetic stirrer and dissolved in THF (2ml). An aqueous solution of HC1 (2M, 1.1 mL, 1.1 eq.) was then added and the resulting mixture cooled to 0°C. Tetrabutylammonium fluoride (TBAF.3H 2 0) (1.0 g, 3.2 mmol, 1.6 eq.) was subsequently added and the reaction mixture was allowed to warm to room temperature and monitored by TLC (eluent: pentane/diethyl ether 90/10). At the end of the reaction (typically lh), the crude mixture was poured over a pad of silica gel (eluent: pentane/diethyl ether 90/10) without work up to afford the title compound as a white solid (Y = 80%). ¾ NMR 500 MHz (CDCb) δ (ppm): 9.83 (d, J = 1.3 Hz, 1H), 7.50 (m, 1H), 7.19 (m, 1H). 19 F NMR 470 MHz (CDCb) δ (ppm): -125.1. 13 C NMR 101 MHz (CDCb) δ (ppm): 182.2 (d, J = 2.2 Hz), 158.1 (d, J = 262.2 Hz), 141.1 (d, J = 4.9 Hz), 124.3 (d, J = 24.4 Hz), 113.9 (d, J = 20.6 Hz). T m : 39°C.

[00153] Synthesis of 4-fluoro-5-( dimethyloctylsilyl)-2-thiophenecarbonitrile (8)

[00154] 3-Fluoro-2-(dimethyloctylsilyl)-thiophene (3) (4.185g, 15.37 mmol, 1 eq.) was placed in a dried round-bottom flask with a magnetic stirrer and purged on a Schlenk line. Anhydrous diethyl ether (150 ml) was added and the resulting solution cooled to -80°C. A solution of ft-BuLi (2.5 M in hexanes, 6.75 mL, 16.9 mmol, 1.1 eq.) was then added dropwise and the mixture was reacted for 15 min at -80°C and allowed to warm to 0°C. The mixture was subsequently cooled back down to -80°C followed by the addition of phenyl cyanate (2.40 g, 19.98 mmol, 1.3 eq.) via a syringe. The resulting reaction mixture was then stirred at -80°C for 30 minutes, allowed to warm to 0°C and stirred at this temperature for 2h. The reaction mixture was subsequently quenched with an aqueous NaOH solution (1.0 M) and extracted three times with diethyl ether. The combined organic phases were washed with water and brine, dried over MgS0 4 and concentrated under vacuum. Purification was achieved by silica gel column chromatography (eluent: hexanes/diethyl ether 95/5 v/v) affording the title compound as a colorless oil (Y = 80%). ¾ NMR 500 MHz (CDCb) δ (ppm): 7.34 (s, 1H), 1.34-1.25 (m, 12H), 0.87 (t, J = 7.0 Hz, 3H), 0.83-0.80 (m, 2H), 0.34 (s, 6H). 19 F NMR 470 MHz (CDCb) δ (ppm): -117.7.

[00155] Synthesis of 4-fluoro-2-thiophenecarbonitrile (6)

[00156] 4-Fluoro-2-thiophenecarboxaldehyde (5) (0.56 g, 4.31 mmol, 1 eq.) was placed in a round-bottom flask with a magnetic stirrer and dissolved in N-methyl-2-pyrrolidone (NMP) (2ml). Hydroxylamine hydrochloride (0.36 g, 5.17 mmol, 1.2 eq.) was then added to the solution and the resulting mixture was heated at 145°C until complete consumption of the starting material (typically 3h). At the end of the reaction, the crude mixture was poured over a pad of silica gel (eluent: pentane/diethyl ether 90/10) without work up to afford the title compound as a white solid (Y = 80%). ¾ NMR 400 MHz (CDCb) δ (ppm): 7.37 (dd, J = 1.7, 0.8 Hz, 1H), 7.04 (dd, J = 1.7, 1.1 Hz, 1H). 19 F NMR 470 MHz (CDCb) δ (ppm): -125.9. 13 C NMR 126 MHz (CDCb) δ (ppm): 156.9 (d, J = 261.5 Hz), 126.5 (d, J = 27.1 Hz), 113.4, 111.5 (d, J = 20.9 Hz), 109.3 (d, J = 10.9 Hz). T m : 37°C.

[00157] Synthesis of 4-fluoro-2-thiophenecarbonitrile (6)

[00158] 4-Fluoro-5-(dimethyloctylsilyl)-2-thiophenecarbonitrile (8) (0.592 g, 1.99 mmol, 1 eq.) was placed in a round-bottom flask with a magnetic stirrer and dissolved in THF (2ml). An aqueous solution of HC1 (2M, 1.1 mL, 1.1 eq.) was then added and the resulting mixture cooled to 0°C. Tetrabutylammonium fluoride (TBAF.3H 2 0) (1.0 g, 3.2 mmol, 1.6 eq.) was subsequently added and the reaction mixture was allowed to warm to room temperature and monitored by TLC (eluent: pentane/diethyl ether 90/10). At the end of the reaction (typically 2h), the crude mixture was poured over a pad of silica gel (eluent: pentane/diethyl ether 90/10) without work-up to afford the title compound as a white solid (Y = 85%). ¾ NMR 400 MHz (CDCb) δ (ppm): 7.37 (dd, J = 1.7, 0.8 Hz, 1H), 7.04 (dd, J = 1.7, 1.1 Hz, 1H). 19 F NMR 470 MHz (CDCb) δ (ppm): -125.9. 13 C NMR 126 MHz (CDCb) δ (ppm): 156.9 (d, J = 261.5 Hz), 126.5 (d, J = 27.1 Hz), 113.4, 111.5 (d, J = 20.9 Hz), 109.3 (d, J = 10.9 Hz). T m : 37°C.

[00159] Synthesis of 3,6-(4-fluorothiophen-2-yl)pyrrolo[3,4-clpyrrole-l,4-dione (7)

[00160] A two neck flask equipped with a condenser and an addition funnel was charged with sodium (0.25 g, 10.8 mmol, 1.2 eq.) in 2-methyl-2-butanol (15 mL). The mixture was then heated at 105°C until complete consumption of the sodium. 4-Fluoro-2- thiophenecarbonitrile (6) (1.15 g, 9.04 mmol, 1.0 eq.) dissolved in 2-methyl-2-butanol (5 mL) was then rapidly added to the mixture followed by the slow addition of diisopropyl succinate (0.830 mL, 4.7 mmol, 0.45 eq.) through the addition funnel. The reaction mixture quickly turned purple and was stirred overnight at 105°C. The reaction mixture was then cooled to 65°C, quenched by the addition of a mixture of methanol (30 mL) and acetic acid (10 mL), and followed by heating at 90°C over a period of 30 min. The reaction mixture was subsequently allowed to cool to room temperature, filtered using a Buchner funnel and washed with methanol to afford the title compound (Y = 75%). 1 H NMR 400 MHz (DMSO) δ (ppm): 11.33 (s, 2H), 8.00 (d, J = 1.8 Hz, 2H), 7.65 (d, J = 1.5 Hz, 2H). 19 F NMR 376 MHz (DMSO) δ (ppm): -127.1. 13 C NMR 101 MHz (DMSO) δ (ppm): 161.4, 157 (d, J = 256.5 Hz), 136.2, 129.2 (d, J = 9.8 Hz), 119.3 (d, J = 27.5 Hz), 111.4 (d, J = 21.2 Hz), 109.4.

[00161] Synthesis of 3,6-f4-fluorothiophen-2-yl)pyrrolo[3,4-clpyrrole-l,4-dione (7)

[00162] A two neck flask equipped with a condenser and an addition funnel was charged with sodium (0.299 g, 13.0 mmol, 1.2 eq.) in 2-methyl-2-butanol (20 mL). The mixture was then heated at 105°C until complete consumption of the sodium. 4-Fluoro-5- (dimethyloctylsilyl)-2-thiophenecarbonitrile (8) (3.0 g, 10.1 mmol, 2.1 eq.) dissolved in 2- methyl-2-butanol (5 mL) was then rapidly added to the mixture followed by the slow addition of diisopropyl succinate (0.970 mL, 4.79 mmol, 1.0 eq.) through the addition funnel. The reaction mixture quickly turned purple and was stirred overnight at 105°C. The reaction mixture was then cooled to 65°C, quenched by the addition of a mixture of methanol (30 mL) and acetic acid (10 mL), and followed by heating at 90°C over a period of 2 h. The reaction mixture was subsequently allowed to cool to room temperature, filtered using a Buchner funnel and washed with methanol to afford the title compound (Y = 80%). ¾ NMR 400 MHz (DMSO) δ (ppm): 11.33 (s, 2H), 8.00 (d, J = 1.8 Hz, 2H), 7.65 (d, J = 1.5 Hz, 2H). 19 F NMR 376 MHz (DMSO) δ (ppm): -127.1. 13 C NMR 101 MHz (DMSO) δ (ppm): 161.4, 157 (d, J = 256.5 Hz), 136.2, 129.2 (d, J = 9.8 Hz), 119.3 (d, J = 27.5 Hz), 111.4 (d, J = 21.2 Hz), 109.4.

[00163] Synthesis of 3,6-f4-fluorothiophen-2-yl)-2,5-Bisfdecyl)pyrrolo[3,4- clpyrrole-l,4-dione (M5)

[00164] A two neck flask equipped with a condenser and an addition funnel was charged with compound 7 (0.51 g, 1.51 mmol leq.), anhydrous potassium carbonate (1 g, 4.55 mmol, 3 eq.) and anhydrous DMF (8 mL). The mixture was then heated at 85°C over a period of 30 min followed slow addition of 1-bromodecane (0.632 g, 4.55 mmol, 3 eq.). The reaction mixture was subsequently stirred overnight while at 85°C. After cooling to room temperature, the reaction mixture was quenched with a saturated solution of NH 4 C1 and extracted three times with diethyl ether. The combined organic phases were washed with water and brine, dried over MgS0 4 and concentrated under vacuum. Purification was achieved by silica gel column chromatography (eluent: chloroform/hexanes 65/35) affording the title compound as a purple solid (Y = 40%). ¾ NMR 500 MHz (CDCb) δ (ppm): 8.70 (d, J = 1.7 Hz, 2H), 7.04 (dd, J = 1.6, 0.5 Hz, 2H), 4.05-4.01 (m, 4H), 1.76-1.70 (m, 4H), 1.43-1.25 (m, 28H), 0.87 (t, J = 7 Hz, 6H). 19 F NMR 470 MHz (CDCb) δ (ppm): -126. 13 C NMR 101 MHz (CDCb) δ (ppm): 161.1, 158.7 (d, J = 260.3 Hz), 139.5 (d, J = 3.2 Hz), 128.2 (d, J = 9.3 Hz), 123.9 (d, J = 27.6 Hz), 109.3 (d, J = 21.4 Hz), 108.3, 42.4, 32, 30.1, 29.6, 29.4, 29.3, 27, 22.8, 14.3.

[00165] Synthesis of 3,6-f4-fluorothiophen-2-yl)-2,5-Bisfdodecyl)pyrrolo[3,4- clpyrrole-l,4-dione (M6)

[00166] M6 was synthetized and purified as per the procedure described for M5 using 1-bromododecane instead of 1-bromodecane, affording the title compound as a purple solid (Y = 43%). ¾ NMR 500 MHz (CDCb) δ (ppm): 8.69 (d, J = 1.7 Hz, 2H), 7.04 (dd, J = 1.6, 0.5 Hz, 2H), 4.05-4.01 (m, 4H), 1.77-1.69 (m, 4H), 1.40-1.25 (m, 36H), 0.87 (t, J = 7 Hz, 6H). 19 F NMR 376 MHz (CDCb) δ (ppm): -126. 13 C NMR 101 MHz (CDCb) δ (ppm): 161.1, 158.7 (d, J = 260.2 Hz), 139.5 (d, J = 3.0 Hz), 128.2 (d, J = 9.4 Hz), 123.9 (d, J = 27.5 Hz), 109.3 (d, J = 21.5 Hz), 108.3, 42.4, 32.1, 30.1, 29.8, 29.7, 29.6, 29.5, 29.4, 27, 22.8, 14.3.

[00167] Synthesis of 3,6-bisf4-fluorothiophen-2-yl)-2,5-dihvdro-2,5-di , - hexyldecyl)pyrrolo[3,4-clpyrrole-l,4-dione (M7)

[00168] M7 was synthetized and purified as per the procedure described for M5 using l-bromo-2-hexyldecane instead of 1-bromodecane, affording the title compound as a purple solid (Y = 28%). ¾ NMR 500 MHz (CDCb) δ (ppm): 8.63 (d, J = 1.7 Hz, 2H), 7.04-7.01 (m, 2H), 3.98 (d, J = 7.8 Hz, 4H), 1.91 (d, J = 7.7 Hz, 2H), 1.35-1.17 (m, 48H), 0.85 (m, 12H). 19 F NMR 470 MHz (CDCb) δ (ppm): -126.26. 13 C NMR 126 MHz (CDCb) δ (ppm): 161.3, 158.4 (d, J = 260.2 Hz), 139.8 (d, J = 2.8 Hz), 128.2 (d, J = 9.4 Hz), 123.7 (d, J = 27.3 Hz), 108.9 (d, J = 21.3 Hz), 108.4, 46.3, 37.8, 31.8, 31.7, 31.1 , 29.9, 29.6, 29.5,

29.3, 26.2, 26.1 , 22.7, 22.6, 14.2, 14.0.

[00169] Synthesis of 3,6-bisf4-fluorothiophen-2-yl)-2,5-dihvdro-2,5-dif7 , - decylnonadecyl)pyrrolo[3,4-clpyrrole-l,4-dione (MS)

[00170] M8 was synthetized and purified as per the procedure described for M5 using l-bromo-7-decylnonadecane instead of 1-bromodecane, affording the title compound as a purple solid (Y = 28%). ¾ NMR 500 MHz (CDCb) δ (ppm): 8.72 (dd, J = 1.7, 0.7 Hz, 2H), 7.05 (d, J = 1.7 Hz, 2H), 4.07-4.02 (m, 4H), 1.74 (p, J = 7.8 Hz, 4H), 1.41 (d, J = 7.6 Hz, 2H), 1.26 (s, 96H), 0.91-0.86 (m, 12H). 19 F NMR 470 MHz (CDCb) δ (ppm): - 125.93. 13 C NMR 101 MHz (CDCb) δ (ppm): 160.9, 158.5 (d, J = 260.3 Hz), 139.4 (d, J = 3.1 Hz), 128.1 (d, J = 9.4 Hz), 123.8 (d, J = 27.5 Hz), 109.1 (d, J = 21.2 Hz), 108.2, 42.3,

37.4, 33.6, 31.9, 30.1 , 30.0, 29.7, 29.3, 26.9, 26.7, 26.6, 22.7, 14.1.

[00171] Synthesis of 3,6-bisf4-fluorothiophen-2-yl)-2,5-dihvdro-2,5-di , - decyltetradecyl)pyrrolo[3,4-clpyrrole-l,4-dione (M9)

[00172] M9 was synthetized and purified as per the procedure described for M5 using l-bromo-2-decyltetradecane instead of 1-bromodecane, affording the title compound as a purple solid (Y = 26%). ¾ NMR 400 MHz (CDCb) δ (ppm): 8.64 (d, J = 1.7 Hz, 2H), 7.04-7.00 (m, 2H), 3.97 (d, J = 7.7 Hz, 4H), 1.90 (s, 2H), 1.37-1.15 (m, 68H), 0.87 (m, 12H). 19 F NMR 376 MHz (CDCb) δ (ppm): -126.21. 13 C NMR 126 MHz (CDCb) δ (ppm): 161.3, 158.4 (d, J = 260.3 Hz), 139.8 (d, J = 2.7 Hz), 128.2 (d, J = 9.2 Hz), 123.7 (m, J = 27.5, 14.2 Hz), 109.0 (m, J = 20.7 Hz), 108.4, 46.3, 37.8, 31.9, 31.2, 29.9, 29.7, 29.6, 29.5, 29.4, 29.3, 26.2, 22.7, 14.2, 14.1.

[00173] Synthesis of 3,6-bisf5-bromo-4-fluorothiophen-2-yl)-2,5-dihvdro-2,5-di , - decyltetradecyl)pyrrolo[3,4-clpyrrole-l,4-dione (M10)

[00174] A 25 mL round bottom flask covered by an aluminum foil was charged with compound M9 (560 mg, 0.554 mmol) and anhydrous CHCb (10 mL). The resulting solution was cooled to 0°C and left to stir for 15 min. N-Bromosuccinimide (208 mg, 1.164 mmol) was subsequently added in several portions over a period of 30 min. The reaction mixture was left to warm overnight and the resulting purple solution added to water and extracted with chloroform. The organic phase was subsequently washed with water and brine, dried over MgS0 4 and concentrated under vacuum (5-10 mL). Purification was achieved by silica gel column chromatography (eluent: chloroform) affording the title compound as a purple solid (Y = 70%). ¾ NMR 500 MHz (CDCb) δ (ppm): 8.57 (s, 2H), 3.91 (d, J = 7.7 Hz, 4H), 1.87 (s, 2H), 1.28-1.22 (m, 68H), 0.87 (m, 12H). 19 F NMR 376 MHz (CDCb) δ (ppm): -124.5. 13 C NMR 126 MHz (CDCb) δ (ppm): 161.2, 156.6 (d, J = 261.8 Hz), 139.2 (d, J = 3.1 Hz), 127.8 (d, J = 9.2 Hz), 123.4 (m, J= 26.5), 108.6, 46.5, 37.9, 32.1, 30.1, 29.8, 29.7, 29.6, 29.5, 29.4, 29.3, 22.8, 14.1.

[00175] Synthesis of 3,6-bisf4-fluorothiophen-2-yl)-2,5-dihvdro-2,5-di , - octyldodecyl)pyrrolo[3,4-clpyrrole-l,4-dione (Mil)

[00176] Mil was synthetized and purified as per the procedure described for M5 using l-bromo-2-octyldodecane instead of 1-bromodecane, affording the title compound as a purple solid (Y = 24%). *H NMR (500 MHz, CDCb) δ (ppm) 8.64 (d, J = 1.7 Hz, 2H), 7.04 - 7.00 (m, 2H), 3.97 (d, J = 7.8 Hz, 4H), 1.91 (d, J = 8.2 Hz, 2H), 1.35 - 1.13 (m, 64H), 0.86 (m, 12H). 19 F NMR (470 MHz, CDCb) δ (ppm) -126.22. 13 C NMR (126 MHz, CDCb) δ (ppm) 161.3, 158.3 (d, J = 260.0 Hz), 139.7 (d, J = 2.8 Hz), 128.1 (d, J = 9.3 Hz), 123.7 (d, J = 27.5 Hz), 108.9 (d, J = 21.4 Hz), 108.4, 46.2, 37.8, 31.9, 31.8, 31.2, 31.1, 30.0, 29.7, 29.6, 29.5, 29.4, 29.3, 29.9, 26.1, 22.6, 14.1.

[00177] Synthesis of 3,6-bisf5-bromo-4-fluorothiophen-2-yl)-2,5-dihvdro-2,5-dif7 , - decylnonadecyl)pyrrolo[3,4-clpyrrole-l,4-dione (M12)

[00178] A 25 mL round bottom flask covered by an aluminum foil was charged with compound M8 (200 mg, 0.174 mmol) and anhydrous CHCb (10 mL). The resulting solution was cooled to 0°C and left to stir for 15 min. N-Bromosuccinimide (65 mg, 0.365 mmol) was subsequently added in several portions over a period of 30 min. The reaction mixture was left to warm overnight and the resulting purple solution added to water and extracted with chloroform. The organic phase was subsequently washed with water and brine, dried over MgS0 4 and concentrated under vacuum (5-10 mL). Purification was achieved by silica gel column chromatography (eluent: chloroform) affording the title compound as a purple solid (Y = 78%). ¾ NMR (400 MHz, CDCb) δ (ppm) 8.63 (s, 2H), 4.00-3.94 (m, 4H), 1.71 (p, J = 7.7 Hz, 4H), 1.40 (d, J = 7.7 Hz, 4H), 1.23 (m, 94H), 0.93 - 0.83 (m, 12H). 19 F NMR (376 MHz, CDCb) δ (ppm) -124.27. 13 C NMR (101 MHz, CDCb) δ (ppm) 160.7, 156.7 (d, J = 261.6 Hz), 138.6 (d, J = 3.1 Hz), 127.5 (d, J = 9.0 Hz), 123.2 (d, J = 26.4 Hz), 108.3, 99.0, 42.3, 37.3, 33.6, 31.9, 30.1, 30.0, 29.7, 29.6, 29.38, 26.8, 26.6, 26.5, 22.7, 14.1.

[00179] Synthesis of polymers by direct heteroarylation polymerization (DHAP) [00180] Synthesis of P2

[00181] A microwave vial holding a magnetic stirring bar was charged with M6 (0.082 mmol, leq.), M4 (0.082 mmol, leq.), tra¾y-bis(acetate)bis[o-(di-o- tolylphosphino)benzyl]dipalladium (II) (2%> mol), tris(2-methoxyphenyl)phosphine (8%> mol), CS2CO3 (3 eq.) and pivalic acid (leq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene was subsequently added (C = 0.2 mol.l "1 , 0.4 ml) and the microwave vial was heated at 120°C using a slow temperature ramp. After heating for 16 hours, additional degassed and anhydrous toluene was added (0.2 mL). Four hours later the reaction was cooled to 65°C, followed by the addition of 1,2,4-trichlorobenzene (TCB) (1 mL). The reaction mixture was then poured into methanol/acidified water (10% HCl; 9: 1 ratio), and the solid polymer recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes, dichloromethane and then chloroform. The chloroform fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 73%>). [00182] Synthesis of P3

[00183] A microwave vial holding a magnetic stirring bar was charged with Ml (0.167 mmol, leq.), M2 (0.167 mmol, leq.), tris(dibenzylideneacetone)dipalladium(0) (Pd 2 dba3) (4% mol), tris(2-cycloheptyloxyphenyl)phosphine (BuraPhos) (20 % mol), K 2 C0 3 (40 eq.) and pivalic acid (leq.) were put in a microwave vial with a magnetic stirring bar. The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous THF was subsequently added (C = 0.1 mol.l "1 , 1.7 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, followed by the addition of 1,2,4- trichlorobenzene (TCB) (1 mL). The reaction mixture was then poured into methanol/acidified water (10% HCl; 9: 1 ratio), and the solid polymer recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and then chloroform. The chloroform fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 91%). 1 H NMR 500 MHz (TCE at 100°C) δ (ppm): 9.03, 8.20, 7.87, 7.65, 4.72, 4.24, 2.41, 2.14, 1.94, 1.58, 1.51, 1.39, 1.25, 0.97, 0.88.

[00184] Synthesis of P4

[00185] A microwave vial holding a magnetic stirring bar was charged with Ml (0.131 mmol, leq.), M5 (0.131 mmol, leq.), Pd(OAc) 2 (4% mol), tris(2- methoxyphenyl)phosphine (16%> mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous THF was subsequently added (C = 0.1 mol.l "1 , 1.3 ml) and the microwave vial was heated at 100°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, followed by the addition of 1,2,4- trichlorobenzene (TCB) (1 mL). The reaction mixture was then poured into methanol/acidified water (10% HCl; 9: 1 ratio), and the solid polymer recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and then chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 80%).

[00186] Synthesis of P5

[00187] A microwave vial holding a magnetic stirring bar was charged with Ml (0.139 mmol, leq.), M5 (0.139 mmol, leq.), Pd(OAc) 2 (4% mol), tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) (16%> mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous THF was subsequently added (C = 0.1 mol.l "1 ,

1.4 ml) and the microwave vial was heated at 100°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, followed by the addition of 1,2,4-trichlorobenzene (TCB) (1 mL). The reaction mixture was then poured into methanol/acidified water (10% HCl; 9: 1 ratio), and the solid polymer recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and then chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μπι nylon filter and dried under vacuum (Y = 85%>).

[00188] Synthesis of P6

[00189] A microwave vial holding a magnetic stirring bar was charged with M7 (0.15 mmol, leq.), 1 ,4-dibromobenzene (0.15 mmol, 1 eq.), Pd(OAc) 2 (5%> mol), tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) (15%> mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous THF was subsequently added (C = 0.1 mol.l "1 ,

1.5 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, and poured into methanol/acidified water (10% HCl; 9: 1 ratio). The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and then chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 8%).

[00190] Synthesis of P7

[00191] A microwave vial holding a magnetic stirring bar was charged with M9 (0.198 mmol, leq.), 1 ,4-dibromobenzene (0.198 mmol, 1 eq.), Pd(OAc) 2 (5% mol), tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) (15% mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous THF was subsequently added (C = 0.1 mol.l "1 , 2.0 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, and poured into methanol/acidified water (10% HC1; 9: 1 ratio). The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and then chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 88%).

[00192] Synthesis of P8

[00193] A microwave vial holding a magnetic stirring bar was charged with M8 (0.169 mmol, leq.), 1 ,4-dibromobenzene (0.169 mmol, 1 eq.), Pd(OAc) 2 (5% mol), tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) (15% mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous THF was subsequently added (C = 0.1 mol.l "1 , 1.7 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, and poured into methanol/acidified water (10% HC1; 9: 1 ratio). The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and then chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 75%). [00194] Synthesis of P9

[00195] A microwave vial holding a magnetic stirring bar was charged with M8 (0.104 mmol, 1 eq.), 3,8-dibromo-6-octyloxyphenanthridine (0.104 mmol, 1 eq.), Pd(PPh3) 2 Cl2 (5% mol), tris(2-cycloheptyloxyphenyl)phosphine (BuraPhos) (15% mol), CS2CO3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene was subsequently added (C = 0.1 mol.l "1 , 1.0 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction was cooled to 65°C, and poured into methanol/acidified water (10% HC1; 9: 1 ratio). The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes, chlorobenzene and o-dichlorobenzene. The o-dichlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 77%).

[00196] Synthesis of PlO

[00197] A microwave vial holding a magnetic stirring bar was charged with Mil (0.120 mmol, leq.), 3,8-dibromo-6-octyloxyphenanthridine (0.042 mmol, 0.35 eq.), 3,8-dibromo- 5-octylphenanthridin-6-one (0.078 mmol, 0.65eq.), Pd(PPh 3 ) 2 Cl 2 (5% mol), tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) (15%> mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene was subsequently added (C = 0.1 mol.l "1 , 1.2 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction mixture was cooled to 65°C, and poured into methanol/acidified water (10% HC1; 9: 1 ratio). The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes, dichloromethane and chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μιη nylon filter and dried under vacuum (Y = 66%).

[00198] Synthesis of Pll

[00199] A microwave vial holding a magnetic stirring bar was charged with M8 (0.175 mmol, leq.), 3,8-dibromo-6-octyloxyphenanthridine (0.061 mmol, 0.35 eq.), 3,8-dibromo- 5-octylphenanthridin-6-one (0.114 mmol, 0.65 eq.), Pd(PPh 3 )2Cl 2 (5% mol), tris(2- cycloheptyloxyphenyl)phosphine (BuraPhos) (15% mol), Cs 2 C0 3 (3 eq.) and pivalic acid (1 eq.). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene was subsequently added (C = 0.1 mol.l "1 , 1.75 ml) and the microwave vial was heated at 120°C (reaction under pressure) until gelation of the reaction mixture. The reaction mixture was cooled to 65°C, and poured into methanol/acidified water (10% HC1; 9:1 ratio). The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and chlorobenzene. The chlorobenzene fraction was reduced to 5-10 mL and then poured into methanol. The purified polymer was recovered by filtration using a 0.45 μπι nylon filter and dried under vacuum (Y = 33%).

[00200] Synthesis of P12

[00201] A microwave vial holding a magnetic stirring bar was charged with M12 (100.9 mg, 0.0793 mmol), 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (39 mg; 0.0793 mmol), Pd 2 (dba) 3 (2.2 mg, 3 mol%) and PPh 3 (2.5 mg, 12 mol%). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene (3.5 mL) and DMF (0.4 mL) were subsequently added (C = 0.02 mol.l "1 ) and the microwave vial was heated at 115°C (reaction under pressure) over a period of 12 h. The reaction mixture was cooled to 65°C and the polymer precipitated by pouring the reaction mixture into methanol. The solid polymer was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and chloroform. The chloroform fraction was reduced to 5 mL and then poured into methanol. The precipitate was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently dried under vacuum (Y = 90%). M n = 40 kg/mol; Mw = 104 kg/mol; PDI = 2.6.

[00202] Synthesis of P13

[00203] A microwave vial holding a magnetic stirring bar was charged with 3,6-bis(5- bromo-4-fluorothiophen-2-yl)-2,5-dihydro-2,5-di(2'-decyltetr adecyl)pyiTolo[3,4-c]pyrrole- 1,4-dione (89.6 mg, 0.0768 mmol), 2,5-bis(trimethylstannyl)thieno[3,2-6]thiophene (35.8 mg; 0.0768 mmol), Pd 2 (dba) 3 (2.1 mg, 3 mol%) and PPh 3 (2.4 mg, 12 mol%). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene (3.5 mL) and DMF (0.4 mL) were subsequently added (C = 0.02 mol.l "1 ) and the microwave vial was heated at 115°C (reaction under pressure) over a period of 15 min. The reaction mixture was cooled to 65°C and the polymer precipitated by pouring the reaction mixture into methanol. The solid polymer was recovered by filtration using a 0.45 μπι nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and chloroform. The chloroform fraction was reduced to 5 mL and then poured into methanol. The precipitate was recovered by filtration using a 0.45 μπι nylon filter. The polymer was subsequently dried under vacuum (Y = 14%). M n = 35 kg/mol; M w = 154 kg/mol; PDI = 4.4.

[00204] Synthesis of P14

[00205] A microwave vial holding a magnetic stirring bar was charged with 3,6-bis(5- bromo-thiophen-2-yl)-2,5-dihydro-2,5-di(2'-decyltetradecyl)p yrrolo[3,4-c]pyrrole-l,4- dione (0.5 eq., 38.8 mg, 0.0343 mmol), 3,6-bis(5-bromo-4-fluorothiophen-2-yl)-2,5- dihydro-2,5-di(2'-decyltetradecyl)pyrrolo[3,4-c]pyrrole-l,4- dione (0.5 eq., 40.0 mg, 0.0343 mmol), 2,5-bis(trimethylstannyl)thieno[3,2-6]thiophene (leq, 31.9 mg; 0.0685 mmol), Pd 2 (dba) 3 (1.9 mg, 3 mol%>) and PPh 3 (2.2 mg, 12 mol%>). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene (3.1 mL) and DMF (0.4 mL) were subsequently added (C = 0.02 mol.l "1 ) and the microwave vial was heated at 115°C (reaction under pressure) over a period of 15 min. The reaction mixture was cooled to 65°C and the polymer precipitated by pouring the reaction mixture into methanol. The solid polymer was recovered by filtration using a 0.45 μπι nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and chloroform. The chloroform fraction was reduced to 5 mL and then poured into methanol. The precipitate was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently dried under vacuum (Y = 20%). M n = 62 kg/mol; Mw = 293 kg/mol; PDI = 4.7.

[00206] Synthesis of P15

[00207] A microwave vial holding a magnetic stirring bar was charged with 3,6-bis(5- bromo-thiophen-2-yl)-2,5-dihydro-2,5-di(2'-decyltetradecyl)p yrrolo[3,4-c]pyrrole-l,4- dione (0.75 eq., 116.3mg, 0.1028 mmol), 3,6-bis(5-bromo-4-fluorothiophen-2-yl)-2,5- dihydro-2,5-di(2'-decyltetradecyl)pyrrolo[3,4-c]pyrrole-l,4- dione (0.25 eq., 40.0 mg, 0.0343 mmol), 2,5-bis(trimethylstannyl)thieno[3,2-6]thiophene (1 eq., 63.8 mg; 0.1371 mmol), Pd 2 (dba)3 (3.8 mg, 3 mol%) and PPh 3 (4.3 mg, 12 mol%). The vial was then sealed with a cap and purged with nitrogen to remove oxygen (repeated 3 times). Degassed and anhydrous toluene (6.2 mL) and DMF (0.7 mL) were subsequently added (C = 0.02 mol.l "1 ) and the microwave vial was heated at 115°C (reaction under pressure) over a period of 15 min. The reaction mixture was cooled to 65°C and the polymer precipitated by pouring the reaction mixture into methanol. The solid polymer was recovered by filtration using a 0.45 μπι nylon filter. The polymer was subsequently washed using a Soxhlet apparatus using acetone, hexanes and chloroform. The chloroform fraction was reduced to 5 mL and then poured into methanol. The precipitate was recovered by filtration using a 0.45 μιη nylon filter. The polymer was subsequently dried under vacuum (Y = 7%). M n = 57 kg/mol; M w = 279 kg/mol; PDI = 4.9.

[00208] While the present disclosure has been described with reference to specific examples, it is to be understood that the disclosure is not limited to the disclosed examples. To the contrary, the disclosure is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. [00209] All publications, patents and patent applications cited in the present disclosure are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.

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