title: 3-D coordination polymers based on the tetrathiafulvalenetetracarboxylate (TTF-TC) derivative: synthesis, characterization, and oxidation issues.
abstract: The reactivity of the redox-active tetracarboxylic acid derived from the tetrathiafulvalene (TTF-TC)H(4) with alkaline cations (K, Rb, Cs) is reported. The exploration of various experimental parameters (temperature, pH) led to the formation of four crystalline three-dimensional coordination polymers formulated M(2)(TTF-TC)H(2) (M = K, Rb, Cs), denoted MIL-132(K), MIL-133(isostructural K, Rb), and MIL-134(Cs). Thermogravimetric analysis and thermodiffraction show that all of the solids are thermally stable up to 150-200 degrees C in the air. In order to exploit the possibility of oxidation of the organic linker in TTF-based compounds, they were employed as positive electrodes in a classical lithium cell. A highly reversible cyclability was achieved at high current density (10 C) with a reasonable performance (approximately 50 mAh g(-1)). Finally, combined electro-(sub)hydrothermal synthesis was used to prepare a fifth 3-D coordination polymer formulated K(TTF-TC)H(2) (denoted MIL-135(K)), this time not based on the neutral TTF-TC linker but its radical, oxidized form TTF-TC(+*). This solid is less thermally stable than its neutral counterparts but exhibits a semiconducting behavior, with a conductivity at room temperature of about 1 mS cm(-1).
authors.affiliation: Institut Lavoisier, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035 Versailles cedex, France.
authors.forename: Thi Le Anh
authors.initials: Tle A
authors.lastname: Nguyen
authors.forename: Rezan
authors.initials: R
authors.lastname: Demir-Cakan
authors.forename: Thomas
authors.initials: T
authors.lastname: Devic
authors.forename: Mathieu
authors.initials: M
authors.lastname: Morcrette
authors.forename: Tim
authors.initials: T
authors.lastname: Ahnfeldt
authors.forename: Pascale
authors.initials: P
authors.lastname: Auban-Senzier
authors.forename: Norbert
authors.initials: N
authors.lastname: Stock
authors.forename: Anne-Marie
authors.initials: AM
authors.lastname: Goncalves
authors.forename: Yaroslav
authors.initials: Y
authors.lastname: Filinchuk
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Tarascon
authors.forename: Gérard
authors.initials: G
authors.lastname: Férey