Catalytic C–H Arylation of Tetrathiafulvalenes for the Synthesis of Functional Materials

Yorimitsu, Hideki; Yoshimura, Aya; Misaki, Yohji

doi:10.1055/s-0040-1707256

Cited by 16 publications

(6 citation statements)

References 24 publications

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“…In 2011, a straightforward synthesis method was developed for aryl TTFs using Pd(OAc) 2 ‐catalyzed direct C−H arylation, which does not require the preparation of metallated precursors (Scheme 1d) [6] . With the emergence of these reactions, many attractive TTF derivatives have been synthesized and systematically investigated in terms of electrochemical and optical properties [7,8] . In this account, we present the synthesis of molecules using the Pd‐catalyzed reactions and analyze the resulting structures, and electrochemical and optical properties.…”

Section: Introductionmentioning

confidence: 99%

Periphery Modification of Tetrathiafulvalenes: Recent Development and Applications

Yoshimura

Misaki

2021

The Chemical Record

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Tetrathiafulvalene (TTF) and its analogs are fascinating molecules in materials science based on their excellent electron‐donating abilities. This personal account describes recent advances in the synthesis of TTF analogs for functional materials via the palladium‐catalyzed modification of peripheries of TTF analogs. We first consider three types of molecules: fluorophore‐TTF hybrid molecules, multi‐redox systems, and an organic ligand for metal‐organic frameworks. These molecules were successfully synthesized via Stille coupling or palladium‐catalyzed direct C−H arylation and their structural, electrochemical, and optical properties were clarified. Subsequently, phosphorus‐substituted TTF analogs were successfully synthesized for future applications of redox‐active phosphine ligands for metal catalysts. The development of these molecules can significantly affect the advancement of chemical science.

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Section: Introductionmentioning

confidence: 99%

Periphery Modification of Tetrathiafulvalenes: Recent Development and Applications

Yoshimura

Misaki

2021

The Chemical Record

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“…Compounds 1 and 2 were efficiently synthesized using Pd-catalyzed direct C–H arylation reported by one of the authors (Scheme ). − TTF reacted with 4-bromotriphenylamine via four-fold C–H arylation reactions under the catalysis of Pd(OAc) 2 /P t Bu 3 to produce 1 in 46% yield. The Pd-catalyzed peripheral arylation was also found to be applicable to EBDT.…”

Section: Resultsmentioning

confidence: 99%

“…All reactions were conducted under an argon atmosphere. Compounds 1 and 2 were synthesized using Pd-catalyzed direct C–H arylation. − The synthetic scheme of 2 is shown in Scheme as a representative. Pd(OAc) 2 (14.1 mg, 0.0628 mmol), P t Bu 3 ·HBF 4 (52.6 mg, 0.181 mmol), and Cs 2 CO 3 (395.5 mg, 1.214 mmol) were placed in a 25 mL reaction flask under an argon atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Improvement in Cycle Life of Organic Lithium-Ion Batteries by In-Cell Polymerization of Tetrathiafulvalene-Based Electrode Materials

Yoshimura

Hemmi

Moriwaki

et al. 2022

ACS Appl. Mater. Interfaces

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Redox-active organic molecules are promising candidates for next-generation electrode materials. Nevertheless, finding low-molecular-weight organic materials with a long cycle life remains a crucial challenge. Herein, we demonstrate the application of tetrathiafulvalene and its vinyl analogue bearing triphenylamines as long-cycle-life electrodes for lithium-ion batteries (LIBs). These molecules were successfully synthesized using palladium-catalyzed C–H arylation. Electrochemical analysis revealed that a polymer formed on the electrode. LIBs comprising these molecules exhibited noteworthy charge–discharge properties with a long cycle life (the capacity after 100 cycles was greater than 90% of the discharge capacity in the third cycle) and a high utilization ratio (approximately 100%). “In-cell” polymerization during the first charge process is considered to contribute to the effect. This study indicates new avenues for the creation of organic materials for rechargeable batteries.

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“…[3][4][5][6][7] More recently and since the pioneering study reporting the palladium-catalysed direct C-H arylation, 8 tetraarylated TTFs have been employed for the construction of functional porous frameworks 9 such as Metal-Organic Frameworks (MOFs), [10][11][12] Covalent Organic Frameworks (COFs) 13,14 or Hydrogen-bonded Organic Frameworks (HOFs). 15,16 However, direct C-H arylation has been limited to TTF derivatives, 17 and the catalytic peripheral modification of other π-extended TTF cores is encouraged for the construction of electroactive frameworks exhibiting new electronic properties and functions.…”

Section: Introductionmentioning

confidence: 99%

Direct C-H arylation of dithiophene-tetrathiafulvalene: tuneable electronic structure and 2D self-assembled molecular networks at the solid/liquid interface

Ribeiro

Valente

Espinosa

et al. 2022

Preprint

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Tetrathiafulvalene is among the most well-known building block in molecular electronics due to its outstanding electron-donating and redox properties. Among its derivatives, dithiophene-tetrathiafulvalene (DT-TTF) received a lot of interest for organic electronics due to its high charge mobility. Herein we report the direct C-H arylation of DT-TTF (1) to synthesise mono- (2, 3) and tetraarylated (4, 5) derivatives bearing different functional groups. The incorporation of electron-donor or electron-withdrawing groups into the DT-TTF core allows the fine-tuning of its electronic structure as demonstrated by cyclic voltammetry, UV-vis spectroscopy and DFT calculations. The self-assembly of DT-TTF-tetrabenzoic acid (5) derivative was studied using scanning tunneling microscopy which revealed the formation of ordered, densely packed 2D hydrogen-bonded networks at the graphite/liquid interface. Importantly, molecule 5 can reach a planar geometry on the graphite surface due to van der Waals interactions with the surface and H-bonding with neighbouring molecules. This work demonstrates a simple method for synthesising arylated DT-TTF derivatives with tuneable molecular orbital energy levels and the formation of 2D networks on the surface, allowing the construction of extended electroactive frameworks based on DT-TTF building blocks.

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Catalytic C–H Arylation of Tetrathiafulvalenes for the Synthesis of Functional Materials

Cited by 16 publications

References 24 publications

Periphery Modification of Tetrathiafulvalenes: Recent Development and Applications

Periphery Modification of Tetrathiafulvalenes: Recent Development and Applications

Improvement in Cycle Life of Organic Lithium-Ion Batteries by In-Cell Polymerization of Tetrathiafulvalene-Based Electrode Materials

Direct C-H arylation of dithiophene-tetrathiafulvalene: tuneable electronic structure and 2D self-assembled molecular networks at the solid/liquid interface

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