Redox-Active Two-Dimensional Tetrathiafulvalene-Copper Metal–Organic Framework with Boosted Electrochemical Performances for Supercapatteries
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Abstract:
Metal-organic frameworks (MOFs) have attracted noticeable attention as promising candidates for electrochemical energy storage. However, the lack of electrical conductivity and the weak stability of most MOFs result in poor electrochemical performances. Here, a tetrathiafulvalene (TTF)-based complex, formulated as [(CuCN)2(TTF(py)4)] (1) (TTF-(py)4 = tetra(4-pyridyl)-TTF), is assembled by in situ generation of coordinated CN- from a nontoxic source. Single-crystal X-ray diffraction analysis reveals that compound 1 possesses a two-dimensional layered planar structure, which is further stacked in parallel to form a three-dimensional supramolecular framework. The planar coordination environment of 1 is the first example of a TTF-based MOF. Attributed to the unique structure and redox TTF ligand, the electrical conductivity of 1 is significantly increased by 5 orders of magnitude upon iodine treatment. The iodine-treated 1 (1-ox) electrode displays typical battery-type behavior through electrochemical characterizations. The supercapattery based on the 1-ox positrode and AC negatrode presents a high specific capacity of 266.5 C g-1 at a specific current of 1 A g-1 with a remarkable specific energy of 62.9 Wh kg-1 at a specific power of 1.1 kW kg-1. The excellent electrochemical performance of 1-ox is one of the best among those reported supercapatteries, demonstrating a new strategy for developing MOF-based electrode materials.Keywords:
Tetrathiafulvalene
M. Brøndsted Nielsen and J. Becher, Chem. Commun., 1998, 475 DOI: 10.1039/A707026H
Tetrathiafulvalene
Acceptor
Electron acceptor
Electron donor
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A simple one-step procedure is reported for the preparation of tetrakis(benzoylthio)tetrathiafulvalene (2) using octacarbonyldicobalt. The crystal structure of 2 is discussed and the preparation of some charge-transfer salts of 2 and their electrical conductivity has been determined. The use of 2 as a synthon for functionalised bis(ethylenedithio)tetrathiafulvalene derivatives is described.
Tetrathiafulvalene
Synthon
Crystal (programming language)
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A novel type of cyclic multi-tetrathiafulvalene (TTF) derivatives is described, including a number of new highly functionalized TTF building blocks. The modular and convergent synthetic methodology allows the sequential assembling of each building block leading to the desired tris-, tetrakis- and pentakis(tetrathiafulvalene) macrocycles 10, 13 and 14 in excellent yields.
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Novel silver(I) complexes 1 and 2 derived from tetrakis(methylthio)tetrathiafulvalene (TMTTTF) and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), respectively, were prepared by the self-assembly approach. Their crystal structures were determined. Complex 1 shows a three-dimensional structure with an unprecedented 4.16-net porous inorganic layer of silver nitrate. In complex 2, silver(I) is coordinated to the BEDT-TTF+ cation and an extended 1D "zig-zag" chain is formed. The electrical conducting properties of complex 1 (after oxidation by iodine) and complex 2 were investigated.
Tetrathiafulvalene
Silver salts
Silver nitrate
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1,3,5,8-Tetrathianaphthalene (2, TTN; 1,4,5,8-tetrathiatetralin) has been synthesized in one step from 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (1) and cis-dichloroethylene in high yield. TTN (2) is readily converted into tetrathiafulvalene (2, TTF) upon tetralithiation or bis(ethylenedithio)tetrathiafulvalene (4, BEDT-TTF) upon tetralithiation, sulfur insertion into the carbon-lithium bond pairs and subsequent capping of the reactive intermediate with 1,2-dibromoethane. The rearrangement of TTN allows for a facile synthesis of TTF and a novel non-coupling route to BEDT-TTF.
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Abstract The synthesis of the dichalcogenane derivatives of MET, (1,3-dioxan-2-yl)methylenedithio(ethylenedithio)tetrathiafulvalene (DOA-MET) and (1,3-dithian-2-yl)methylenedithio(ethylenedithio)tetrathiafulvalene (DTA-MET), and the preparation of their charge-transfer (CT) materials are investigated to explore new organic metals. The resulting (DOA-MET)3AuI2 salt exhibits weak metallic conducting behavior, and has screwed donor stacks.
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Radical ion
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Abstract A series of tetrakis(n-alkyltelluro)tetrathiafulvalene (TTeCn-TTF) was synthesized where n ranges from 1 to 18. Some chemical and physical properties of TTeCn-TTF were studied and compared with those of the sulfur analogues; tetrakis(n-alkylthio)tetrathiafulvalene (TTCn-TTF).
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A series of novel heterocycle-fused TTF-type electron donors, bis(propylenethio)tetrathiafulvalene (BPT-TTF, 5), bis(propyleneseleno)tetrathiafulvalene (BPS-TTF, 6), and their tetraselenafulvalene analogues (BPT-TSF, 7 and BPS-TSF, 8) have been effectively synthesized from a common starting compound, THP-protected pent-4-yn-1-ol. The solution electrochemistry reveals that all the new donors have good electron donating properties. Formation of their radical cation salts by electrocrystallization technique has been successfully achieved. All the radical salts derived from the TTF derivatives (5 and 6) are insulating owing to the complete charge transfer. On the other hand, the TSF derivatives (7 and 8) afford different types of highly conductive radical cation salts. Of these, 7·PF6, 7·AsF6 and 7·FeCl4 remain metallic down to liquid helium temperature.
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Radical ion
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