3-D Coordination polymers based on the tetrathiafulvalenetetracarboxylate (TTF-TC) derivative: Synthesis, characterization, and oxidation issues
(2010) Inorganic Chemistry — Vol. 49, n° 15, p. 7135-7143 (2010)
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- 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 °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 (∼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. © 2010 American Chemical Society.
- Affiliations
ESRF, Grenoble (France) Chimie
Citations
Nguyen, T. L. A., Demir-Cakan, R., Devic, T., Morcrette, M., Ahnfeldt, T., Auban-Senzier, P., Stock, N., Goncalves, A.-M., Filinchuk, Y., Tarascon, J.-M., & Férey, G. (2010). 3-D Coordination polymers based on the tetrathiafulvalenetetracarboxylate (TTF-TC) derivative: Synthesis, characterization, and oxidation issues. Inorganic Chemistry, 49(15), 7135-7143. https://doi.org/10.1021/ic100950n (Original work published 2010)