Benzothiadiazole and its π-extended, heteroannulated derivatives: useful acceptor building blocks for high-performance donor–acceptor polymers in organic electronics

AbstractIn organic electronics, an aromatic fused ring is a basic unit that provides π-electrons to construct semiconductors and governs the device performance. The main challenge in developing new π-skeletons for tuning the material properties is the limitation of the available chemical approach. Herein, we successfully synthesize two pentacyclic siloxy-bridged π-conjugated isomers to investigate the synergistic effects of Si and O atoms on the geometric and electronic influence of π-units in organic electronics. Notably, the synthesis routes for both isomers possess several advantages over the previous approaches for delivering conventional aromatic fused-rings, such as environmentally benign tin-free synthesis and few synthetic steps. To explore their potential application as photovoltaic materials, two isomeric acceptor–donor–acceptor type acceptors based on these two isomers were developed, showing a decent device efficiency of 10%, which indicates the great potential of this SiO-bridged ladder-type unit for the development of new high-performance semiconductor materials.

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Effects of the Electron-Deficient Third Components in n-Type Terpolymers on Morphology and Performance of All-Polymer Solar Cells

Organic Materials ◽

10.1055/s-0040-1713857 ◽

2020 ◽

Vol 02 (03) ◽

pp. 214-222

Author(s):

Bin Liu ◽

Huiliang Sun ◽

Chang Woo Koh ◽

Mengyao Su ◽

Bao Tu ◽

...

Keyword(s):

Solar Cells ◽

High Performance ◽

Noncovalent Interactions ◽

Polymer Solar Cells ◽

Energy Levels ◽

Building Blocks ◽

The Third ◽

Donor Acceptor ◽

And Performance ◽

P Type

Compared with p-type terpolymers, less effort has been devoted to n-type analogs. Herein, we synthesized a series of n-type terpolymers via incorporating three electron-deficient third components including thienopyrroledione (TPD), phthalimide, and benzothiadiazole into an imide-functionalized parent n-type copolymer to tune optoelectronic properties without sacrificing the n-type characteristics. Due to effects of the third components with different electron-accepting ability and solubility, the resulting three polymers feature distinct energy levels and crystallinity. In addition, heteroatoms (S, O, and N) attached on the third components trigger intramolecular noncovalent interactions, which can increase molecule planarity and have a significant effect on the packing structures of the polymer films. As a result, the best power conversion efficiency of 8.28% was achieved from all-polymer solar cells (all-PSCs) based on n-type terpolymer containing TPD. This is contributed by promoted electron mobility and face-on polymer packing, showing the pronounced advantages of the TPD used as a third component for thriving efficient n-type terpolymers. The generality is also successfully validated in a benchmark polymer donor/acceptor system by introducing TPD into the benchmark n-type polymer N2200. The results demonstrate the feasibility of introducing suitable electron-deficient building blocks as the third components for high-performance n-type terpolymers toward efficient all-PSCs.

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Linking design and properties of purine-based donor–acceptor chromophores as optoelectronic materials

Journal of Materials Chemistry C ◽

10.1039/c7tc01835e ◽

2017 ◽

Vol 5 (27) ◽

pp. 6891-6898 ◽

Cited By ~ 8

Author(s):

Graham S. Collier ◽

Lauren A. Brown ◽

Evan S. Boone ◽

Meesha Kaushal ◽

M. Nance Ericson ◽

...

Keyword(s):

Organic Electronics ◽

Building Blocks ◽

Important Task ◽

Optoelectronic Materials ◽

Conjugated Systems ◽

Donor Acceptor

Creating new building blocks for donor–acceptor conjugated systems is an important task for continued development of materials for organic electronics.

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C–H Arylation of Unsubstituted Furan and Thiophene with Acceptor Bromides: Access to Donor–Acceptor–Donor-Type Building Blocks for Organic Electronics

The Journal of Organic Chemistry ◽

10.1021/jo502432e ◽

2014 ◽

Vol 80 (2) ◽

pp. 980-987 ◽

Cited By ~ 57

Author(s):

Rukiya Matsidik ◽

Johannes Martin ◽

Simon Schmidt ◽

Johannes Obermayer ◽

Florian Lombeck ◽

...

Keyword(s):

Organic Electronics ◽

Building Blocks ◽

Donor Type ◽

Donor Acceptor

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Exploring the “Goldilocks Zone” of Semiconducting Polymer Photocatalysts via Donor-Acceptor Interactions

10.26434/chemrxiv.6210110.v1 ◽

2018 ◽

Cited By ~ 1

Author(s):

Yaroslav S. Kochergin ◽

Dana Schwarz ◽

Amitava Acharjya ◽

Arun Ichangi ◽

Ranjit Kulkarni ◽

...

Keyword(s):

High Performance ◽

Building Blocks ◽

Semiconducting Polymer ◽

High Performance Polymer ◽

Covalently Bonded ◽

Catalytic Sites ◽

Donor Acceptor ◽

Energy Economy ◽

Microporous Organic Polymers ◽

Optical Bandgaps

Water splitting using polymer photocatalysts is a key technology to a truly sustainable hydrogen-based energy economy. Synthetic chemists have intuitively tried to enhance photocatalytic activity by tuning the length of π-conjugated domains of their semiconducting polymers, but the increasing flexibility and hydrophobicity of ever-larger organic building blocks leads to adverse effects such as structural collapse and inaccessible catalytic sites. To reach the ideal optical bandgap of ~2.3 eV, we synthesised a library of eight sulphur and nitrogen containing porous polymers (SNPs) with similar geometries but with optical bandgaps ranging from 2.07 to 2.60 eV using Stille coupling. These polymers combine π-conjugated electron-withdrawing triazine- (C3N3) and electron donating, sulphur-containing moieties as covalently-bonded donor-acceptor frameworks with permanent porosity. The remarkable optical properties of SNPs enable fluorescence on-off sensing of volatile organic compounds and illustrate intrinsic charge-transfer effects. Moreover, obtained polymers effectively evolve H2 gas from water under visible light irradiation with hydrogen evolution rates up to 3158 µmol h-1 g-1 and high apparent quantum efficiency which is the highest value obtained for microporous organic polymers to-date. The design principles demonstrated here are transferable to a new field of high-performance polymer photocatalysts based on efficient donor-acceptor dyads.

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Conjugated Polymers Containing Building Blocks 1,3,4,6-Tetraarylpyrrolo[3,2-b]pyrrole-2,5-dione (isoDPP), Benzodipyrrolidone (BDP) or Naphthodipyrrolidone (NDP): A Review

Polymers ◽

10.3390/polym11101683 ◽

2019 ◽

Vol 11 (10) ◽

pp. 1683 ◽

Cited By ~ 3

Author(s):

Zhifeng Deng ◽

Taotao Ai ◽

Rui Li ◽

Wei Yuan ◽

Kaili Zhang ◽

...

Keyword(s):

Conjugated Polymers ◽

High Performance ◽

Electronic Device ◽

Building Blocks ◽

Electrochemical Characteristics ◽

The Novel ◽

Synthesis Properties ◽

Device Applications ◽

Donor Acceptor ◽

Better Than

π-Conjugated organic donor–acceptor (D–A) type polymers are widely developed and used in electronic device. Among which, diketopyrrolopyrrole (DPP)-based polymers have received the most attention due to their high performances. The novel chromophores named 1,3,4,6-tetraarylpyrrolo[3,2-b]pyrrole-2,5-dione (isoDPP), benzodipyrrolidone (BDP) and naphthodipyrrolidone (NDP) are resemble DPP in chemical structure. IsoDPP is an isomer of DPP, with the switching position of carbonyl and amide units. The cores of BDP and NDP are tri- and tetracyclic, whereas isoDPP is bicyclic. π-Conjugation extension could result polymers with distinct optical, electrochemical and device performance. It is expected that the polymers containing these high-performance electron-deficient pigments are potential in the electronic device applications, and have the potential to be better than the DPP-based ones. IsoDPP, BDP, and NDP based polymers are synthesized since 2011, and have not receive desirable attention. In this work, the synthesis, properties (optical and electrochemical characteristics), electronic device as well as their relationship depending on core-extension or structure subtle optimization have been reviewed. The final goal is to outline a theoretical scaffold for the design the D–A type conjugated polymers, which is potential for high-performance electronic devices.

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Exploring the “Goldilocks Zone” of Semiconducting Polymer Photocatalysts via Donor-Acceptor Interactions

10.26434/chemrxiv.6210110 ◽

2018 ◽

Author(s):

Yaroslav S. Kochergin ◽

Dana Schwarz ◽

Amitava Acharjya ◽

Arun Ichangi ◽

Ranjit Kulkarni ◽

...

Keyword(s):

High Performance ◽

Building Blocks ◽

Semiconducting Polymer ◽

High Performance Polymer ◽

Covalently Bonded ◽

Catalytic Sites ◽

Donor Acceptor ◽

Energy Economy ◽

Microporous Organic Polymers ◽

Optical Bandgaps

Water splitting using polymer photocatalysts is a key technology to a truly sustainable hydrogen-based energy economy. Synthetic chemists have intuitively tried to enhance photocatalytic activity by tuning the length of π-conjugated domains of their semiconducting polymers, but the increasing flexibility and hydrophobicity of ever-larger organic building blocks leads to adverse effects such as structural collapse and inaccessible catalytic sites. To reach the ideal optical bandgap of ~2.3 eV, we synthesised a library of eight sulphur and nitrogen containing porous polymers (SNPs) with similar geometries but with optical bandgaps ranging from 2.07 to 2.60 eV using Stille coupling. These polymers combine π-conjugated electron-withdrawing triazine- (C3N3) and electron donating, sulphur-containing moieties as covalently-bonded donor-acceptor frameworks with permanent porosity. The remarkable optical properties of SNPs enable fluorescence on-off sensing of volatile organic compounds and illustrate intrinsic charge-transfer effects. Moreover, obtained polymers effectively evolve H2 gas from water under visible light irradiation with hydrogen evolution rates up to 3158 µmol h-1 g-1 and high apparent quantum efficiency which is the highest value obtained for microporous organic polymers to-date. The design principles demonstrated here are transferable to a new field of high-performance polymer photocatalysts based on efficient donor-acceptor dyads.

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Vinylene-bridged difluorobenzo[c][1,2,5]-thiadiazole (FBTzE): a new electron-deficient building block for high-performance semiconducting polymers in organic electronics

Journal of Materials Chemistry C ◽

10.1039/c8tc05764h ◽

2019 ◽

Vol 7 (4) ◽

pp. 905-916 ◽

Cited By ~ 2

Author(s):

Yuya Asanuma ◽

Hiroki Mori ◽

Ryosuke Takahashi ◽

Yasushi Nishihara

Keyword(s):

Organic Electronics ◽

Building Block ◽

High Performance ◽

Semiconducting Polymers ◽

New Class

A new class of an acceptor unit, vinylene-bridged 5,6-difluorobenzothiadiazole FBTzE, and three FBTzE-containing copolymers has been synthesized and characterized.

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Progress in Organic Crystal Transistors for High-Performance Organic Electronics

10.1557/proc-1115-h05-64 ◽

2008 ◽

Author(s):

Jun Takeya ◽

Takafumi Uemura ◽

M. Uno ◽

Masakazu Yamagishi ◽

Yukihiro Tominari

Keyword(s):

Organic Electronics ◽

High Performance ◽

Organic Crystal

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Energetic Control of Redox-Active Polymers Towards Safe Organic Bioelectronic Materials

10.26434/chemrxiv.11366186.v1 ◽

2019 ◽

Author(s):

Alexander Giovannitti ◽

Reem B. Rashid ◽

Quentin Thiburce ◽

Bryan D. Paulsen ◽

Camila Cendra ◽

...

Keyword(s):

Molecular Oxygen ◽

Organic Semiconductors ◽

Side Reaction ◽

Semiconducting Polymers ◽

Side Reactions ◽

Redox Active ◽

Donor Acceptor ◽

Electrochemical Devices ◽

Biological Environment ◽

Device Operation

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side‑products. This is particularly important for bioelectronic devices which are designed to operate in biological systems. While redox‑active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side‑reactions with molecular oxygen during device operation. We show that this electrochemical side reaction yields hydrogen peroxide (H2O2), a reactive side‑product, which may be harmful to the local biological environment and may also accelerate device degradation. We report a design strategy for the development of redox-active organic semiconductors based on donor-acceptor copolymers that prevent the formation of H2O2 during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte‑gated devices in application-relevant environments.

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