Research

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18 pages, 4682 KiB

Open AccessFeature PaperArticle

Theoretical Calculations for Highly Selective Direct Heteroarylation Polymerization: New Nitrile-Substituted Dithienyl-Diketopyrrolopyrrole-Based Polymers

by Thomas Bura, Serge Beaupré, Marc-André Légaré, Olzhas A. Ibraikulov, Nicolas Leclerc and Mario Leclerc

Molecules 2018, 23(9), 2324; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23092324 - 12 Sep 2018

Cited by 7 | Viewed by 4120

Abstract

Direct Heteroarylation Polymerization (DHAP) is becoming a valuable alternative to classical polymerization methods being used to synthesize π-conjugated polymers for organic electronics applications. In previous work, we showed that theoretical calculations on activation energy (E_a) of the C–H bonds were helpful [...] Read more.

Direct Heteroarylation Polymerization (DHAP) is becoming a valuable alternative to classical polymerization methods being used to synthesize π-conjugated polymers for organic electronics applications. In previous work, we showed that theoretical calculations on activation energy (E_a) of the C–H bonds were helpful to rationalize and predict the selectivity of the DHAP. For readers’ convenience, we have gathered in this work all our previous theoretical calculations on E_a and performed new ones. Those theoretical calculations cover now most of the widely utilized electron-rich and electron-poor moieties studied in organic electronics like dithienyl-diketopyrrolopyrrole (DT-DPP) derivatives. Theoretical calculations reported herein show strong modulation of the E_a of C–H bond on DT-DPP when a bromine atom or strong electron withdrawing groups (such as fluorine or nitrile) are added to the thienyl moiety. Based on those theoretical calculations, new cyanated dithienyl-diketopyrrolopyrrole (CNDT-DPP) monomers and copolymers were prepared by DHAP and their electro-optical properties were compared with their non-fluorinated and fluorinated analogues. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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11 pages, 1825 KiB

Open AccessArticle

An Electron-Transporting Thiazole-Based Polymer Synthesized Through Direct (Hetero)Arylation Polymerization

by Patricia Chávez, Ibrahim Bulut, Sadiara Fall, Olzhas A. Ibraikulov, Christos L. Chochos, Jérémy Bartringer, Thomas Heiser, Patrick Lévêque and Nicolas Leclerc

Molecules 2018, 23(6), 1270; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23061270 - 25 May 2018

Cited by 5 | Viewed by 4195

Abstract

In this work, a new n-type polymer based on a thiazole-diketopyrrolopyrrole unit has been synthesized through direct (hetero)arylation polycondensation. The molar mass has been optimized by systematic variation of the the monomer concentration. Optical and electrochemical properties have been studied. They clearly [...] Read more.

In this work, a new n-type polymer based on a thiazole-diketopyrrolopyrrole unit has been synthesized through direct (hetero)arylation polycondensation. The molar mass has been optimized by systematic variation of the the monomer concentration. Optical and electrochemical properties have been studied. They clearly suggested that this polymer possess a high electron affinity together with a very interesting absorption band, making it a good non-fullerene acceptor candidate. As a consequence, its charge transport and photovoltaic properties in a blend with the usual P3HT electron-donating polymer have been investigated. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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10 pages, 1494 KiB

Open AccessArticle

Synthesis of a 1,2-Dithienylethene-Containing Donor-Acceptor Polymer via Palladium-Catalyzed Direct Arylation Polymerization (DArP)

by Masayuki Wakioka, Natsumi Yamashita, Hiroki Mori, Yasushi Nishihara and Fumiyuki Ozawa

Molecules 2018, 23(4), 981; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23040981 - 23 Apr 2018

Cited by 17 | Viewed by 5632

Abstract

This paper reports the synthesis of D-A polymers containing 1,2-dithienylethene (DTE) units via palladium-catalyzed direct arylation polymerization (DArP). The reaction of dibromoisoindigo (1-Br) and DTE (2-H), in the presence of Pd₂(dba)₃·CHCl [...] Read more.

This paper reports the synthesis of D-A polymers containing 1,2-dithienylethene (DTE) units via palladium-catalyzed direct arylation polymerization (DArP). The reaction of dibromoisoindigo (1-Br) and DTE (2-H), in the presence of Pd₂(dba)₃·CHCl₃ (0.5 mol%), P(2-MeOC₆H₄)₃ (L1) (2 mol%), pivalic acid (1 equiv) as catalyst precursors, and Cs₂CO₃ (3 equiv) as a base affords poly(1-alt-2) with a high molecular weight (M_n up to 44,900). Although, it has been known that monomers, with plural C–H bonds, tend to form insoluble materials via direct arylation at undesirable C–H positions; the reaction of 1-Br and 2-H cleanly proceeds without insolubilization. The resulting polymer has a well-controlled structure and exhibits good charge transfer characteristics in an organic field-effect transistor (OFET), compared to the polymer produced by Migita–Kosugi–Stille cross-coupling polymerization. The DArP product displays an ideal linear relationship in the current–voltage curve, whereas the Migita–Kosugi–Stille product shows a V_G-dependent change in the charge mobility. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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10 pages, 1229 KiB

Open AccessFeature PaperArticle

Direct (Hetero)Arylation Polymerization of a Spirobifluorene and a Dithienyl-Diketopyrrolopyrrole Derivative: New Donor Polymers for Organic Solar Cells

by Pierre Josse, Sergey Dayneko, Yangqian Zhang, Sylvie Dabos-Seignon, Shiming Zhang, Philippe Blanchard, Gregory C. Welch and Clément Cabanetos

Molecules 2018, 23(4), 962; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23040962 - 20 Apr 2018

Cited by 12 | Viewed by 5485

Abstract

The synthesis and preliminary evaluation as donor material for organic photovoltaics of the poly(diketopyrrolopyrrole-spirobifluorene) (PDPPSBF) is reported herein. Prepared via homogeneous and heterogeneous direct (hetero)arylation polymerization (DHAP), through the use of different catalytic systems, conjugated polymers with comparable molecular weights were [...] Read more.

The synthesis and preliminary evaluation as donor material for organic photovoltaics of the poly(diketopyrrolopyrrole-spirobifluorene) (PDPPSBF) is reported herein. Prepared via homogeneous and heterogeneous direct (hetero)arylation polymerization (DHAP), through the use of different catalytic systems, conjugated polymers with comparable molecular weights were obtained. The polymers exhibited strong optical absorption out to 700 nm as thin-films and had appropriate electronic energy levels for use as a donor with PC₇₀BM. Bulk heterojunction solar cells were fabricated giving power conversion efficiencies above 4%. These results reveal the potential of such polymers prepared in only three steps from affordable and commercially available starting materials. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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17 pages, 14063 KiB

Open AccessFeature PaperArticle

Direct (Hetero)Arylation for the Synthesis of Molecular Materials: Coupling Thieno[3,4-c]pyrrole-4,6-dione with Perylene Diimide to Yield Novel Non-Fullerene Acceptors for Organic Solar Cells

by Thomas A. Welsh, Audrey Laventure and Gregory C. Welch

Molecules 2018, 23(4), 931; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23040931 - 17 Apr 2018

Cited by 28 | Viewed by 5916

Abstract

Herein we report on the synthesis of an N-annulated perylene diimide (PDI) disubstituted thieno[3,4-c]pyrrole-4,6-dione (TPD) molecular acceptor (PDI–TPD–PDI) by direct heteroarylation (DHA) methods. Three sets of DHA conditions that explore the effects of solvent, temperature, and catalyst were employed to find the [...] Read more.

Herein we report on the synthesis of an N-annulated perylene diimide (PDI) disubstituted thieno[3,4-c]pyrrole-4,6-dione (TPD) molecular acceptor (PDI–TPD–PDI) by direct heteroarylation (DHA) methods. Three sets of DHA conditions that explore the effects of solvent, temperature, and catalyst were employed to find the optimal conditions for the synthesis of two PDI–TPD–PDI derivatives. We then selected one PDI–TPD–PDI for use as a non-fullerene acceptor in organic solar cell devices with the donor polymer PBDB-T. Active layer bulk-heterojunction blends were modified using several post-deposition treatments, including thermal annealing, solvent vapour annealing, and high boiling solvent additives. It was found that active layers cast from o-dichlorobenzene with a 3% v/v diphenylether additive yielded films with adequate phase separation, and subsequently gave the best organic solar cell performance, with power conversion efficiencies greater than 3%. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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15 pages, 1798 KiB

Open AccessArticle

Novel Conjugated Polymers Prepared by Direct (Hetero) arylation: An Eco-Friendly Tool for Organic Electronics

by Fuchuan Liu, Yangqian Zhang, Hang Wang and Shiming Zhang

Molecules 2018, 23(2), 408; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23020408 - 13 Feb 2018

Cited by 9 | Viewed by 5002

Abstract

The phthalimide (PhI) moiety has been attracting more attention as an excellent acceptor building block in donor-acceptor (D-A) conjugated polymers. In this paper; three D-A conjugated polymers with or without thiocarbonyl moieties are successfully prepared by the direct (hetero)-arylation polymerization (DHAP), which is [...] Read more.

The phthalimide (PhI) moiety has been attracting more attention as an excellent acceptor building block in donor-acceptor (D-A) conjugated polymers. In this paper; three D-A conjugated polymers with or without thiocarbonyl moieties are successfully prepared by the direct (hetero)-arylation polymerization (DHAP), which is an atom efficient and facile synthetic strategy to obtain polymer materials. Compared with the traditional carbon-carbon coupling reactions, this method possesses more advantages, including: fewer synthetic steps, avoidance of the preparation of the organometallic reagents, higher atom economy and fewer toxic byproducts, better compatibility with chemically sensitive functional groups and so on. All three of these designed PhI-based polymers exhibited favourable optoelectronic and thermal performance. The optical, thermodynamic and electrochemical properties of the synthesized polymers were systematically investigated using ultraviolet-visible (UV-vis) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and cyclic voltammetry (CV). The results of these three polymers indicated that thionation of the carbonyl was a highly effective methods to improve the properties of PhI-based polymers; and provided impetus for the development of thionated PhI derivatives for organic electronic applications. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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2779 KiB

Open AccessArticle

Small Molecules Derived from Thieno[3,4-c]pyrrole-4,6-dione (TPD) and Their Use in Solution Processed Organic Solar Cells

by Cesar Garcias-Morales, Daniel Romero-Borja, José-Luis Maldonado, Arián E. Roa, Mario Rodríguez, J. Pablo García-Merinos and Armando Ariza-Castolo

Molecules 2017, 22(10), 1607; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules22101607 - 30 Sep 2017

Cited by 28 | Viewed by 7747

Abstract

In this work, microwave synthesis, chemical, optical and electrochemical characterization of three small organic molecules, TPA-TPD, TPA-PT-TPD and TPA-TT-TPD with donor-acceptor structure and their use in organic photovoltaic cells are reported. For the synthesis, 5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione was [...] Read more.

In this work, microwave synthesis, chemical, optical and electrochemical characterization of three small organic molecules, TPA-TPD, TPA-PT-TPD and TPA-TT-TPD with donor-acceptor structure and their use in organic photovoltaic cells are reported. For the synthesis, 5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione was used as electron withdrawing fragment while the triphenylamine was used as electron donating fragment. Molecular electronic geometry and electronic distribution density were established by density functional theory (DFT) calculations and confirmed by optical and chemical characterization. These molecules were employed as electron-donors in the active layer for manufacturing bulk heterojunction organic solar cells, where [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) was used as electron-acceptor. As cathode, Field′s metal (FM), an eutectic alloy (Bi/In/Sn: 32.5%, 51%, and 16.5%, respectively) with a melting point above 62 °C, was easily deposited by drop casting under vacuum-free process and at air atmosphere. Prepared devices based on TPA-TPD:PC71BM (1:4 w/w ratio) presented a large V_OC = 0.97 V, with J_SC = 7.9 mA/cm², a FF = 0.34, then, a power conversion efficiency (PCE) of 2.6%. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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Review

Jump to: Research

18 pages, 1555 KiB

Open AccessFeature PaperReview

Performance Comparisons of Polymer Semiconductors Synthesized by Direct (Hetero)Arylation Polymerization (DHAP) and Conventional Methods for Organic Thin Film Transistors and Organic Photovoltaics

by Arthur D. Hendsbee and Yuning Li

Molecules 2018, 23(6), 1255; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23061255 - 24 May 2018

Cited by 19 | Viewed by 4728

Abstract

C-C bond forming reactions are central to the construction of π-conjugated polymers. Classical C-C bond forming reactions such as the Stille and Suzuki coupling reactions have been widely used in the past for this purpose. More recently, direct (hetero)arylation polymerization (DHAP) has earned [...] Read more.

C-C bond forming reactions are central to the construction of π-conjugated polymers. Classical C-C bond forming reactions such as the Stille and Suzuki coupling reactions have been widely used in the past for this purpose. More recently, direct (hetero)arylation polymerization (DHAP) has earned a place in the spotlight with an increasing number of π-conjugated polymers being produced using this atom-economic and more sustainable chemistry. As semiconductors in organic electronics, the device performances of the polymers made by DHAP are of great interest and importance. This review compares the device performances of some representative π-conjugated polymers made using the DHAP method with those made using the conventional C-C bond forming reactions when they are used as semiconductors in organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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13 pages, 4235 KiB

Open AccessFeature PaperReview

Recent Developments in C–H Activation for Materials Science in the Center for Selective C–H Activation

by Junxiang Zhang, Lauren J. Kang, Timothy C. Parker, Simon B. Blakey, Christine K. Luscombe and Seth R. Marder

Molecules 2018, 23(4), 922; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23040922 - 16 Apr 2018

Cited by 41 | Viewed by 6659

Abstract

Organic electronics is a rapidly growing field driven in large part by the synthesis of π-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of π-conjugated molecules and polymers, but the [...] Read more.

Organic electronics is a rapidly growing field driven in large part by the synthesis of π-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of π-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C–H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C–H Functionalization (CCHF), we have been developing C–H activation methodology for the synthesis of π-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of π-conjugated polymers through C–H activation. Full article

(This article belongs to the Special Issue Direct (Hetero)Arylation: A New Tool for Organic Electronics)

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