Non‐symmetric Half‐Fused B←N Coordinated Diketopyrrolopyrrole Building Block for n‐type Semiconducting Polymers

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 6, 2023

The development of conjugated polymers with high semiconducting performance and reliability is great significance for flexible electronics. Herein, we developed a new type electron-accepting building block; i.e., non-symmetric half-fused B←N coordinated diketopyrrolopyrrole (DPP) (HBNDPP), amorphous toward rigid fusion part HBNDPP endows the resulting decent electron transport, while its structure causes polymer to exhibit multiple conformation isomers flat torsional potential energies. Thus, it gets packed in an manner solid state, ensuring good resistance bending strain. Combined hardness softness, organic field-effect transistor devices n-type charge properties mobility, resistance, ambient stability. preliminary study makes this block candidate future design materials electronic devices.

Language: Английский

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An In‐Situ Cyanidation Strategy To Access Tetracyanodiacenaphthoanthracene Diimides with High Electron Mobilities Exceeding 10 cm² V⁻¹ s⁻¹

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: July 3, 2023

Abstract A family of novel highly π‐extended tetracyano‐substituted acene diimides, named as tetracyanodiacenaphthoanthracene diimides (TCDADIs), have been synthesized using a facile four‐fold Knoevenagel condensation strategy. Unlike conventional cyano substitution reactions, our approach enables access to large π‐conjugated backbone with the in‐situ formation four substitutents at room temperature while avoiding extra cyano‐functionalization reactions. TCDADIs decorated different N‐alkyl substituents present good solubility, near‐coplanar backbones, crystallinity, and low‐lying lowest unoccupied molecular orbital energies −4.33 eV, all which contribute desirable electron‐transport performance when applied in organic field‐effect transistors (OFET). The highest electron mobility an OFET based on 2‐hexyldecyl‐substituted TCDADI single crystal reaches 12.6 cm 2 V −1 s , is not only among values for reported n‐type semiconductor materials (OSMs) but also exceeds that most OSMs imide units.

Language: Английский

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Diradicaloid Boron‐Doped Molecular Carbons Achieved by Pentagon‐Fusion

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(51)

Published: Nov. 4, 2023

Molecular carbons (MCs) are molecular cutouts of carbon materials. Doping with heteroatoms and constructing open-shell structures two powerful approaches to achieve unexpected unique properties MCs. Herein, we disclose a new strategy design boron-doped MCs (BMCs), namely by pentagon-fusion an organoborane π-system. We synthesized diradicaloid BMC molecules that feature C24 B C38 π-skeletons containing pentagonal ring. A thorough investigation reveals such not only leads their local antiaromaticity, but also incorporates internal quinoidal substructure thereby induces singlet diradical states. Moreover, fully fused enable efficient π conjugation, which is expanded over the whole frameworks. Consequently, some intriguing physical achieved, as narrow energy gaps, very broad light absorptions, superior photothermal capability, along excellent photostability. Notably, solid molecule exhibits absorption covers range 300-1200 nm efficiency 93.5 % for solar-driven water evaporation, thus demonstrating potential BMCs high-performance organic

Language: Английский

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Photonic Modulation Enabled by Controlling the Edge Structures of Boron‐Doped Molecular Carbons

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 24, 2023

Abstract Control over topological edges of molecular carbons (MCs) is importance for achieving diverse topologies and desirable physical properties. However, it remains very challenging heteroatom‐doped MCs due to the synthetic difficulty. Herein, we report control edge structures boron‐doped (BMCs) via sequential cyclization strategy. Three BMC molecules that feature C 56 B 2 or 84 polycyclic π‐skeletons with selective cove/fjord cove/bay edges, respectively, were synthesized through rational combination Mallory photoreaction Scholl reaction. We not only obtain largest π‐system reported so far, but also disclose fine their length greatly affects electronic thereby photonic properties BMCs, such as tunable aromaticity, decreased band gaps, well redshifted absorptions fluorescence. Remarkably, molecule exhibits stimulated emission behavior amplified spontaneous property, both which have never been pristine π‐systems, thus demonstrating potential BMCs optical gain materials laser cavities.

Language: Английский

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Dithienoazepine‐Based Near‐Infrared Dyes: Janus‐Faced Effects of a Thiophene‐Fused Structure on Antiaromatic Azepines

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Sept. 13, 2023

We here disclose that the incorporation of thiophene rings into a seven-membered 8π azepine in fused fashion produces useful antiaromatic core for near-infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno-fused electron-accepting groups adopt flat conformations ground state. The exhibited broad absorption spectra cover visible region as well sharp emission bands NIR region, which are considerably red-shifted relative those dibenzo-fused congeners. Theoretical study revealed two contradictory effects less-aromatic thiophene-fused structure, i.e., enhancement antiaromaticity adjacent ring and relief through contribution quinoidal resonance form. combination dithienoazepine cationic produced fluorescent dye an at 878 nm solution.

Language: Английский

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