Very Small Bandgap π-Conjugated Polymers with Extended Thienoquinoids

Kawabata, Kohsuke; Saito, Masahiko; Osaka, Itaru; Takimiya, Kazuo

doi:10.1021/jacs.6b03688

Cited by 116 publications

(90 citation statements)

References 62 publications

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“…In all of the cases, the branched parts are decyl and dodecyl groups. 3-Decylpentadecan-1-ol (3DP-OH), 4-decylhexadecan-1-ol (4DH-OH), and 5-decylheptadecan-1-ol (5DH-OH) were synthesized from 2-decyl-1-tetradecyl bromide (2DT-Br) via the formation of the Grignard reagent followed by treatment with paraformaldehyde, 29 ethylene oxide, 30 and oxetane, 31 respectively. These alkyl alcohols were brominated to afford the corresponding bromides (that is, 3-decyl-1-pentadecyl bromide (3DP-Br), 4-decyl-1-hexadecyl bromide (4DH-Br), and 5-decyl-1-heptadecyl bromide (5DH-Br)).…”

Section: Resultsmentioning

confidence: 99%

Effects of branching position of alkyl side chains on ordering structure and charge transport property in thienothiophenedione- and quinacridone-based semiconducting polymers

Kawabata

Saito

Takemura

et al. 2016

Polym J

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To investigate the effect of the branching position of the alkyl groups on the side chain of semiconducting polymers, we synthesized two series of semiconducting polymers based on thienothiophene-2,5-dione (PTTD4Ts) and quinacridone (PQA2Ts). 2-Decyltetradecyl, 3-decylpentadecyl, 4-decylhexadecyl, and 5-decylheptadecyl groups were used, and the branching position was systematically varied from the second carbon from the backbone to the fifth carbon. These branched side chains are introduced into the thiophene ring for PTTD4Ts and the quinacridone unit for PQA2Ts. The polymer thin films exhibited small but clear differences in their optical absorption spectra, suggesting that the intermolecular interaction in the solid state varied based on the branching position. The grazing incident X-ray diffraction study revealed that the π-π stacking d-spacing of both polymers decreased when the branching position was moved away from the backbones, indicating that the intermolecular interaction was enhanced. Therefore, regardless of the core where the alkyl groups were introduced, the branching position effectively improved the ordering structure of the polymers, which was most likely due to suppressed steric hindrance. Although PTTD4Ts did not exhibit a clear correlation between the branching position and charge carrier mobility, the mobility of PQA2Ts gradually increased as the branching position moved away from the backbone.

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Section: Resultsmentioning

confidence: 99%

Effects of branching position of alkyl side chains on ordering structure and charge transport property in thienothiophenedione- and quinacridone-based semiconducting polymers

Kawabata

Saito

Takemura

et al. 2016

Polym J

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“…7173 As summarized in Table 6, the copolymers with the thiophene-based comonomer unit generally (P2P7) afforded ambipolar OFETs, whereas the polymers with electron deficient units (P8P10) and with ethene as an electronically "neutral" unit (P1) afforded n-type unipolar OFETs. For the ambipolar polymers (P2P7)-based OFETs, electron mobility tends to be affected by the size of donor units, as larger ones brought lower electron mobility, 54,77 (except the case of P2 with the thiophene-comonomer), while the hole mobility showed no clear trend depending on the donor unit. This is likely explained by the influence of crystallinity and molecular orientation on the mobility in the thin-film state.…”

Section: ¹1mentioning

confidence: 99%

“…For this reason, the electron/ hole mobility of ambipolar polymers, which is closely related to intermolecular LUMO-LUMO/HOMO-HOMO overlap, respectively, is affected by the relative size of each building unit. 54,77 In P8P10, the LUMO delocalizes over the polymer backbone, thus making the mobility less sensitive to the comonomer unit. On the other hand, small but non-negligible dependence of electron mobility on the alkyl groups on the imide nitrogen atoms were observed for P10 (for 2-decyltetradecyl derivative, ® e : 9.6 © 10 ¹2 cm 2 V ¹1 s ¹1 , for 3-decylpentadecyl derivative, ® e : 0.31 cm 2 V ¹1 s ¹1 ).…”

Section: ¹1mentioning

confidence: 99%

Thiophene-Fused Naphthalene Diimides: New Building Blocks for Electron Deficient π-Functional Materials

Takimiya

Nakano

2017

Bulletin of the Chemical Society of Japan

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Development of novel π-conjugated building blocks that can be integrated into molecular or macromolecular systems is key to the evolution of new superior organic semiconductors utilized as the active materials in organic electronics devices such as organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and organic thermoelectric (TE) devices. This review affords a brief overview of thiophene-fused naphthalene diimide (NDI), namely naphtho[2,3-b:6,7-b¤]dithiophene diimide (NDTI) and naphtho [2,3-b]thiophene diimide (NTI), recently developed as novel electron deficient building blocks for n-type and ambipolar organic semiconductors. These thiophene-fused NDI building blocks had not been known until 2013 owing to their synthetic difficulty; more precisely, the difficulty in attaching fused-thiophene ring(s) on the NDI core. We have successfully established a thiophene-annulation reaction on ethyne-substituted NDI derivatives, which allows us to elaborate various NDTI and NTI derivatives. The key features of these building blocks are low-lying energy levels of lowest unoccupied molecular orbitals (LUMO, 3.84.1 eV below the vacuum level) and easy functionalizability of the thiophene ¡-positions, which allows their derivatives and polymers to conjugate efficiently with additional π-and comonomer units. These features make the NDTI-and NTIderivatives and polymers promising n-type and ambipolar materials for OFETs and acceptors for OPVs. In fact, various useful materials have already been derived from the NDTI and NTI building blocks: air-stable n-type small molecules and polymers with high electron mobility (³0.8 cm 2 V ¹1 s ¹1), ambipolar oligomers and polymers with well-balanced hole and electron mobilities, doped n-type semiconductors affording bulk conductors applicable to n-type TE materials, and electron acceptor molecules and polymers for OPVs showing promising power conversion efficiencies of up to 9%. These impressive and diversified device performances testify the usefulness of thiophene-fused NDI building blocks in the development of new electron deficient π-functional materials.

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“…Molecules with narrow bandgaps below 1.5 eV absorbing in the IR/NIR are produced by extending conjugation in the molecular structure designs . The concept of alternating electron donating‐electron accepting (ED‐EA) units is now widely employed to tune the HOMO‐LUMO bandgap and optoelectronic properties of conjugated molecules and can serve the purpose of producing low bandgap active materials . The building blocks for these copolymers are generally 5 or 6 member aromatic rings which can include heteroatoms.…”

Section: Active Materials For Visibly Transparent Psc Fabricationmentioning

confidence: 99%

Can Polymer Solar Cells Open the Path to Sustainable and Efficient Photovoltaic Windows Fabrication?

Vohra

2018

The Chemical Record

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Sunlight is among the most abundant energy sources available on our planet. Finding adequate solutions to properly and efficiently harvest it is of major importance to potentially solve the global energy crisis. Polymer solar cells have been introduced in the late 20th century as low‐cost and easily processed alternative to the state‐of‐the‐art silicon photovoltaics. Their power conversion efficiencies, which were initially rather low, are constantly improving and now reach values close to 15 %. As their optical properties can be easily tuned, designing active layer which absorb homogeneously throughout the visible spectrum is relatively simple. These peculiar characteristics enable the possibility to fabricate visibly transparent solar cells with high color rendering indices which can be employed as photovoltaic windows. After reviewing some of the most successful examples of polymer solar cell‐based transparent photovoltaic window fabrication, I will discuss the possibility to produce these devices in a sustainable and/or eco‐friendly manner while maintaining their performances.

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Very Small Bandgap π-Conjugated Polymers with Extended Thienoquinoids

Cited by 116 publications

References 62 publications

Effects of branching position of alkyl side chains on ordering structure and charge transport property in thienothiophenedione- and quinacridone-based semiconducting polymers

Effects of branching position of alkyl side chains on ordering structure and charge transport property in thienothiophenedione- and quinacridone-based semiconducting polymers

Thiophene-Fused Naphthalene Diimides: New Building Blocks for Electron Deficient π-Functional Materials

Can Polymer Solar Cells Open the Path to Sustainable and Efficient Photovoltaic Windows Fabrication?

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