This work was supported by an INTAS Grant (Project 00-0651), the Russian Foundation for Basic Research (Projects 02-02-17063, 03-02-06362, 03-03-32207, 03-03-06231), DGI-Spain (Project BFM2000-1312-C02-01) and Generalitat de Catalunya (Project 2001 SGR 333). We thank the X-Ray Structural Center, Russian Academy of Sciences (Institute of Organoelement Compounds, RAS, Moscow) for access to X-ray equipment to collect the experimental data for the crystals 1 and 2.
New Organic Metals Based on BDH-TTP Radical Cation Salts with the Photochromic Nitroprusside Anion [FeNO(CN)5]2–†
Article first published online: 22 JUL 2004
Copyright © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Advanced Functional Materials
Volume 14, Issue 7, pages 660–668, July, 2004
How to Cite
Shevyakova, I., Buravov, L., Tkacheva, V., Zorina, L., Khasanov, S., Simonov, S., Yamada, J., Canadell, E., Shibaeva, R. and Yagubskii, E. (2004), New Organic Metals Based on BDH-TTP Radical Cation Salts with the Photochromic Nitroprusside Anion [FeNO(CN)5]2–. Adv. Funct. Mater., 14: 660–668. doi: 10.1002/adfm.200305170
- Issue published online: 22 JUL 2004
- Article first published online: 22 JUL 2004
- Manuscript Received: 8 DEC 2003
- 2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP);
- Molecular conductors;
- Organic metals;
- Transport properties
Three new 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) radical cation salts with the photochromic nitroprusside anion have been synthesized: κ-(BDH-TTP)4[FeNO(CN)5]·NB (1), κ-(BDH-TTP)4[FeNO(CN)5] (2), and (BDH-TTP)2[FeNO(CN)5] (3). The salts were characterized by single-crystal X-ray diffraction, electrical resistance measurements, and electronic band structure calculations. The crystals of 1 and 2 have a layered structure in which the BDH-TTP layers of κ-type alternate with anionic sheets. Solvent (nitrobenzene) molecules are also involved in the composition of the anion sheet of 1. The crystals of 1 have triclinic symmetry and two crystallographically independent BDH-TTP radical cations in the unit cell, while there is only one independent radical cation in the monoclinic structure of 2. The salts 1 and 2 are stable quasi-2D metals down to 4.2 K, while 3, with full charge transfer, is a semiconductor with low conductivity at room temperature. It is suggested that the κ-type layers of BDH-TTP are more robust than those of BEDT-TTF and its derivatives and the consequences for the electronic structure are discussed.