Proton–electron-coupled functionalities of conductivity, magnetism, and optical properties in molecular crystals

Mori, H.; Yokomori, So; Dekura, Shun; Ueda, Akira

doi:10.1039/d1cc06826a

Cited by 12 publications

(18 citation statements)

References 128 publications

(299 reference statements)

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“…The properties of these electrolytes are intriguing given the current understanding in the field of ion conduction mechanisms in the solid state. We note that a series of CT complexes have been reported to show proton conduction. , It is difficult to exclude the possibility of proton/hydroxide transport from the introduction of trace water based on our data. Future research to identify the contributions of individual species (Li + , TFSI – , H + , etc.)…”

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confidence: 67%

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Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries

Yang

Schaefer

2023

ACS Energy Lett.

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Current research on solid-state organic electrolytes mainly focuses on polymer electrolytes where ion transport is facilitated by chain segmental motion. A limited number of prior reports suggest that solid-state electrolytes based on organic chargetransfer (CT) complexes can have surprisingly high ionic conductivity. Here, we report that processing and environmental conditions drastically impact charge transport properties of CT complex electrolytes based on tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Thermal annealing and water vapor treatment decreases electronic conductivity and increases ionic conductivity. The electrolyte with a 1-1-2-0.45 molar ratio of TTF-TCNQ-LiTFSI-H 2 O has an ionic conductivity of 2 × 10 −3 S/cm at 25 °C with order 10 4 times lower electronic conductivity. In this system where ion conduction is decoupled from the mobility of the organic phase, thermal annealing helps reduce CT connectivity and expose more surfaces to interact with LiTFSI, and water promotes the dissociation of LiTFSI.

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confidence: 67%

“…We note that a series of CT complexes have been reported to show proton conduction. 44,45 It is difficult to exclude the possibility of proton/hydroxide transport from the introduction of trace water based on our data. Future research to identify the contributions of individual species (Li + , TFSI − , H + , etc.)…”

mentioning

confidence: 83%

Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries

Yang

Schaefer

2023

ACS Energy Lett.

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“…8–12 Note that although these CT complexes/salts are, in many cases, formed as two- or multiple-component systems involving donors, acceptors, or inorganic ions, single-component organic conductors have also been developed through sophisticated molecular design and crystal engineering. 13–30…”

Section: Introductionmentioning

confidence: 99%

Boundary research between organic conductors and transistors: new trends for functional molecular crystals

Kadoya

Higashino

2023

CrystEngComm

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“…Our group recently developed single-crystalline metal bis(dithiolene) complexes, − including nickel-centered planar structures with catechol substituents . The highly distributed d/π-conjugated systems with fused catechol groups satisfy the HOMO and LUMO levels for ambipolar semiconductors (requirement i), although catechol groups are easily deprotonated upon oxidation.…”

Section: Introductionmentioning

confidence: 99%

Ambipolar Nickel Dithiolene Complex Semiconductors: From One- to Two-Dimensional Electronic Structures Based upon Alkoxy Chain Lengths

et al. 2022

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Air-stable single-component ambipolar organic semiconductors that conduct both holes and electrons are highly desired but have been rarely realized. Neutral nickel bis(dithiolene) complexes are promising candidates that fulfill the stringent electronic requirements of shallow HOMO levels and deep LUMO levels, which can reduce the carrier injection barrier to overcome the work function of gold electrodes and ensure air stability. However, most nickel bis(dithiolene) analogs that have been characterized as ambipolar semiconductors have twisted molecular structures that hinder the effective intermolecular interactions required for carrier conduction. To address this issue, we synthesized planar alkoxy-substituted nickel bis-(dithiolene) analogs that facilitate dense packing with effective intermolecular interactions. Remarkably, changing the methoxy substituents to ethoxy or propoxy groups led to a dramatic change in the packing mode, from one-dimensional to herringbone-like, while maintaining effective intermolecular interactions. These materials overcome the usual trade-off between crystallinity and solubility; they are highly crystalline, even in their film forms, and are highly soluble in organic solvents. They are therefore readily solution-processable to form semiconducting layers with well-defined and well-ordered structures in field-effect transistors. Devices based on these compounds exhibited efficient ambipolar characteristics, even after several months of exposure to air, achieving high carrier mobilities of up to 10 −2 cm 2 V −1 s −1 and large on/off ratios of up to 10 5 , which are the top-class performances achieved for a single-component ambipolar semiconductor material driven in air.

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Proton–electron-coupled functionalities of conductivity, magnetism, and optical properties in molecular crystals

Abstract: This article highlights the recent progress of proton–electron-coupled functionalities based on π- and d/π-electron molecular materials, which will stimulate inspiration for pioneering novel phenomena/functionalities.

Cited by 12 publications

References 128 publications

Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries

Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries

Boundary research between organic conductors and transistors: new trends for functional molecular crystals

Ambipolar Nickel Dithiolene Complex Semiconductors: From One- to Two-Dimensional Electronic Structures Based upon Alkoxy Chain Lengths

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