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Tetrathiafulvalene-Based Conductors Containing Organometallic Components

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Conducting and Magnetic Organometallic Molecular Materials

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 27))

Abstract

Hundreds of cation radical salts containing tetrathiafulvalene (TTF) and its derivatives have been prepared and characterized over the past 50 years. After superconductivity was discovered in salts containing bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), a tremendous international effort was undertaken to prepare cation radical salts containing nearly every imaginable type of anion in a search for new superconducting materials. Surprisingly, only a relatively small number of these salts contained organometallic anions. The use of tetrakis(trifluoromethyl)metallate anions as charge compensating components in BEDT-TTF salts resulted in the discovery of a diverse family of molecular superconductors. More recently, organometallic anions have been utilized as a means to introduce multiple properties into a single material. Halophenylene, metallocarborane and metallocene-type anions have been utilized as components of cation radical salts. Several covalent derivatives of the TTF molecule have also been reported that incorporate organometallic moieties. Due to the diverse nature of organometallic anions and contemporary interest in coupling redox active species to the TTF moiety, it is likely that this field will exhibit significant growth in the years ahead.

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Abbreviations

BEDT-TTF:

Bis(ethylenedithio)tetrathiafulvalene

BETS:

Bis(ethylenedithio)tetraselenafulvalene

Cp:

Cyclopentyldienyl

Cp*:

Pentamethylcyclopentyldienyl

DBCE:

1,2-Dibromo-1-chloroethane

Dca:

Dicyanamide

DDQ:

2,3-Dichloro-5,6-dicyanobenzoquinone

DmitH2 :

4,5-Dimercapto-1,3-dithione-2-thione

EDAX:

Energy dispersive analysis by X-ray

EPR:

Electron paramagnetic resonance

o-Me2TTF:

3,4-Dimethyltetrathiafulvalene

MI:

Metal-to-insulator

PPN:

Bis(triphenylphosphoranylidene)ammonium

Ppy:

C-dehydro-2-phenylpyridine

TBA:

Tetrabutylammonium

TCE:

1,1,2-Trichloroethane

TCNQ:

Tetracyanoquniodimethane

TEA:

Tetraethylammonium

TMA:

Tetramethylammonium

TMTSF:

Bis(tetramethyl)tetraselenafulvalene

TMTTF:

Bis(tetramethyl)tetrathiafulvalene

TTF:

Tetrathiafulvalene

TTFFc:

1-Tetrathiafulvalenylferrocene

TTFPh2 :

4,4′-Diphenyltetrathiafulvalene

VT:

Bis(vinylenedithio)tetrathiafulvalene

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Acknowledgments

Work supported by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357.

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  1. Materials Science Division, Argonne National Laboratory, Argonne, IL, 9700 S. Cass Avenue, Argonne, IL, 60439, USA

    John A. Schlueter

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  1. UMR CNRS 6226, Université de Rennes 1, Rennes CX, 35042, France

    Marc Fourmigué

  2. UMR 6226 CNRS, Université de Rennes 1, av. du Général Leclerc 263, Rennes CX, 35042, France

    Lahcène Ouahab

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Schlueter, J.A. (2009). Tetrathiafulvalene-Based Conductors Containing Organometallic Components. In: Fourmigué, M., Ouahab, L. (eds) Conducting and Magnetic Organometallic Molecular Materials. Topics in Organometallic Chemistry, vol 27. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-00408-7_1

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