N,N′-Unsubstituted Naphthodithiophene Diimide: Synthesis and Derivatization via N-Alkylation and -Arylation

Nakano, Masahiro; Sawamoto, Masanori; Yuki, Mizue; Takimiya, Kazuo

doi:10.1021/acs.orglett.6b01785

Cited by 15 publications

(8 citation statements)

References 41 publications

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“…62 The key feature of the new route was to construct N,N¤-unsubstituted NDTI (6) as a versatile intermediate, which was then converted into N,N¤-dialkyl or diaryl NDTI derivatives. This solved the first and second issues mentioned above.…”

Section: Synthesis Of Ndti and Nti Derivativesmentioning

confidence: 99%

“…In addition, the E LUMO of 2g, which affects the V OC in the OPV devices, can be finely tuned by careful selection of the alkyl groups on the imide nitrogen atoms, those groups being readily introduced via the Mitsunobu reaction with the corresponding alcohol on the NTI core directly (Scheme 6). 62 The BHJ-OPVs composed of 2g and PBDB-T as the donor material showed typical photovoltaic responses (Figure 11 for optimized device characteristics). It is interesting to note that depending on the alkyl groups on the imide nitrogen atoms, the photovoltaic properties were largely affected.…”

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confidence: 99%

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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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Section: Synthesis Of Ndti and Nti Derivativesmentioning

confidence: 99%

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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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“…A similar effect of the branching position of N-alkyl groups on E LUMO was observed in related molecules. 37 This result indicates that the E LUMO of NTI-based acceptors can be controlled by modification of substituents on the imide nitrogen atoms. In contrast to the E LUMO , E HOMO of both IDT-NTIs were almost the same (E HOMO = −5.4 eV), which is consistent with the relatively small contribution of the NTI moieties to the HOMO (Figure S1c).…”

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confidence: 94%

Bis(naphthothiophene diimide)indacenodithiophenes as Acceptors for Organic Photovoltaics

Hamonnet

Nakano

et al. 2017

Chem. Mater.

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“…Polymers with energy levels of the lowest unoccupied molecular orbital ( E LUMO ) lower than −4.0 eV are potential candidates for the development of versatile n-type semiconducting polymers . To realize such low-lying E LUMO , employing or combining π-building block(s) with high electron deficiency in the polymer backbone is a promising strategy. − In this context, naphtho[2,3- b :6,7- b ′]dithiophenediimide (NDTI) − and benzo[1,2- c :4,5- c ′]bis[1,2,5]thiadiazole (BBT) , are among the most electron-deficient building blocks capable of being incorporated into a conjugated polymer backbone. By combining these two building blocks, new polymers PNDTI-BBT-DT and PNDTI-BBT-DP, which have different solubilizing alkyl chains, were designed and synthesized (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Naphthodithiophenediimide–Benzobisthiadiazole-Based Polymers: Versatile n-Type Materials for Field-Effect Transistors and Thermoelectric Devices

et al. 2017

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New π-conjugated polymers with strong electron affinity, PNDTI-BBTs, consisting of naphtho[2,3-b:6,7-b′]dithiophenediimide (NDTI) and benzo[1,2-c:4,5-c′]bis[1,2,5]thiadiazole (BBT) units, were synthesized. PNDTI-BBTs have low-lying LUMO energy levels (∼−4.4 eV), which is sufficiently low for air-stable electron transport in organic field-effect transistors and for being readily doped by a well-known n-dopant, N,N-dimethyl-2-phenyl-2,3-dihydro-1H-benzoimidazole (N-DMBI), affording doped polymer films with relatively high conductivities and Seebeck coefficients. Depending on the solubilizing alkyl groups (2-decyltetradecyl, PNDTI-BBT-DT, or 3-decylpentadecyl groups, PNDTI-BBT-DP), not only the electron mobility in the transistor devices with the pristine polymer thin films (PNDTI-BBT-DT: ∼0.096 cm2 V–1 s–1; PNDTI-BBT-DP: ∼0.31 cm2 V–1 s–1) but also the conductivity and power factor of the doped thins films (PNDTI-BBT-DT: ∼0.18 S cm–1 and ∼0.6 μW m–1 K–2; PNDTI-BBT-DP: ∼5.0 S cm–1 and ∼14 μW m–1 K–2) were drastically changed. The differences in the electric properties were primarily ascribed to the better crystalline nature of the PNDTI-BBT-DP than those of PNDTI-BBT-DT in the thin-film state. Furthermore, UV–vis and ESR spectra demonstrated that doping effectiveness was largely affected by the alkyl groups: the PNDTI-BBT-DP films with better crystalline order prevented overdoping, resulting in ca. 20 times higher conductivity and power factors. From these results, it can be concluded that tuning the intermolecular interaction and consequently obtaining the thin-film with well-ordered polymers by the alkyl side chains is a promising strategy for developing superior thermoelectric materials.

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N,N′-Unsubstituted Naphthodithiophene Diimide: Synthesis and Derivatization via N-Alkylation and -Arylation

Cited by 15 publications

References 41 publications

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

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

Bis(naphthothiophene diimide)indacenodithiophenes as Acceptors for Organic Photovoltaics

Naphthodithiophenediimide–Benzobisthiadiazole-Based Polymers: Versatile n-Type Materials for Field-Effect Transistors and Thermoelectric Devices

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