Title: A Purely Organic Molecular Metal Based on a Hydrogen‐Bonded Charge‐Transfer Complex: Crystal Structure and Electronic Properties of TTF‐Imidazole–<i>p</i>‐Chloranil
Abstract: Angewandte Chemie International EditionVolume 43, Issue 46 p. 6343-6346 Communication A Purely Organic Molecular Metal Based on a Hydrogen-Bonded Charge-Transfer Complex: Crystal Structure and Electronic Properties of TTF-Imidazole–p-Chloranil† Tsuyoshi Murata, Tsuyoshi Murata Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Fax: (+81) 6-6850-5395Search for more papers by this authorYasushi Morita Prof. Dr., Yasushi Morita Prof. Dr. [email protected] Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Fax: (+81) 6-6850-5395 PRESTO, JST, JapanSearch for more papers by this authorKozo Fukui Dr., Kozo Fukui Dr. PRESTO, JST, JapanSearch for more papers by this authorKazunobu Sato Prof. Dr., Kazunobu Sato Prof. Dr. Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, JapanSearch for more papers by this authorDaisuke Shiomi Prof. Dr., Daisuke Shiomi Prof. Dr. Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, JapanSearch for more papers by this authorTakeji Takui Prof. Dr., Takeji Takui Prof. Dr. Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, JapanSearch for more papers by this authorMitsuhiko Maesato Prof. Dr., Mitsuhiko Maesato Prof. Dr. Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, Fax: (+81) 75-753-4035Search for more papers by this authorHideki Yamochi Prof. Dr., Hideki Yamochi Prof. Dr. Research Center for Low Temperature and Materials Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, JapanSearch for more papers by this authorGunzi Saito Prof. Dr., Gunzi Saito Prof. Dr. Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, Fax: (+81) 75-753-4035Search for more papers by this authorKazuhiro Nakasuji Prof. Dr., Kazuhiro Nakasuji Prof. Dr. Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Fax: (+81) 6-6850-5395Search for more papers by this author Tsuyoshi Murata, Tsuyoshi Murata Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Fax: (+81) 6-6850-5395Search for more papers by this authorYasushi Morita Prof. Dr., Yasushi Morita Prof. Dr. [email protected] Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Fax: (+81) 6-6850-5395 PRESTO, JST, JapanSearch for more papers by this authorKozo Fukui Dr., Kozo Fukui Dr. PRESTO, JST, JapanSearch for more papers by this authorKazunobu Sato Prof. Dr., Kazunobu Sato Prof. Dr. Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, JapanSearch for more papers by this authorDaisuke Shiomi Prof. Dr., Daisuke Shiomi Prof. Dr. Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, JapanSearch for more papers by this authorTakeji Takui Prof. Dr., Takeji Takui Prof. Dr. Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, JapanSearch for more papers by this authorMitsuhiko Maesato Prof. Dr., Mitsuhiko Maesato Prof. Dr. Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, Fax: (+81) 75-753-4035Search for more papers by this authorHideki Yamochi Prof. Dr., Hideki Yamochi Prof. Dr. Research Center for Low Temperature and Materials Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, JapanSearch for more papers by this authorGunzi Saito Prof. Dr., Gunzi Saito Prof. Dr. Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, Fax: (+81) 75-753-4035Search for more papers by this authorKazuhiro Nakasuji Prof. Dr., Kazuhiro Nakasuji Prof. Dr. Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Fax: (+81) 6-6850-5395Search for more papers by this author First published: 23 November 2004 https://doi.org/10.1002/anie.200460801Citations: 101 † This work was partially supported by PRESTO-JST, and by 21COE program “Creation of Integrated EcoChemistry of Osaka University”. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Modification of tetrathiafulvalene with an imidazolyl substituent as a hydrogen-bond donor allows the generation of a hydrogen-bonded 2:1 charge-transfer complex with chloranil. This complex forms a three-dimensional network with columnar stacking of each component and multiple S⋅⋅⋅S interactions (see picture). This strongly hydrogen-bonded purely organic conducting material is the first to display metallic behavior. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2004/z460801_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 1aM. R. Bryce, J. Mater. Chem. 1995, 5, 1481; 10.1039/jm9950501481 CASWeb of Science®Google Scholar 1bP. Batail, K. Boubekeur, M. Fourmigué, J.-C. P. Gabriel, Chem. Mater. 1998, 10, 3005. 10.1021/cm980538s CASWeb of Science®Google Scholar 2For a recent overview of H-bonding, see The Weak Hydrogen Bond (Eds.: ), Oxford University Press, New York, 1999, chap. 1. Google Scholar 3Examples of H-bonded TTF derivatives: Hydroxymethyl: Google Scholar 3aP. Blanchard, K. Boubekeur, M. Sallé, G. Duguay, M. Jubault, A. Gorgues, J. D. Martin, E. Canadell, P. Auban-Senzier, D. Jérome, P. Batail, Adv. Mater. 1992, 4, 579. Carboxy: 10.1002/adma.19920040912 CASWeb of Science®Google Scholar 3bA. Dolbecq, M. Fourmigué, P. Batail, Bull. Soc. Chim. Fr. 1996, 133, 83; Amide: CASWeb of Science®Google Scholar 3cK. Heuzé, C. Mézière, M. Fourmigué, P. Batail, C. Coulon, E. Canadell, P. Auban-Senzier, D. Jérome, Chem. Mater. 2000, 12, 1898; 10.1021/cm000143k CASWeb of Science®Google Scholar 3dK. Heuzé, M. Fourmigué, P. Batail, E. Canadell, P. Auban-Senzier, Chem. Eur. J. 1999, 5, 2971; 10.1002/(SICI)1521-3765(19991001)5:10<2971::AID-CHEM2971>3.0.CO;2-S CASWeb of Science®Google Scholar 3eS. A. Baudron, N. Avarvari, P. Batail, C. Coulon, R. Clérac, E. Canadell, P. Auban-Senzier, J. Am. Chem. Soc. 2003, 125, 11 583. Thioamide: 10.1021/ja0356129 CASWeb of Science®Google Scholar 3fA. J. Moore, M. R. Bryce, A. S. Batsanov, J. N. Heaton, C. W. Lehmann, J. A. K. Howard, N. Robertson, A. E. Underhill, I. F. Perepichka, J. Mater. Chem. 1998, 8, 1541. Nucleic acid: 10.1039/a802037j CASWeb of Science®Google Scholar 3gY. Morita, S. Maki, M. Ohmoto, H. Kitagawa, T. Okubo, T. Mitani, K. Nakasuji, Org. Lett. 2002, 4, 2185. Pyrrole-fused: 10.1021/ol020081z CASPubMedWeb of Science®Google Scholar 3hK. Zong, W. Chen, M. P. Cava, R. D. Rogers, J. Org. Chem. 1996, 61, 8117; 10.1021/jo961282h CASPubMedWeb of Science®Google Scholar 3iJ. O. Jeppesen, K. Takimiya, F. Jensen, T. Brimert, K. Nielsen, N. Thorup, J. Becher, J. Org. Chem. 2000, 65, 5794; 10.1021/jo000742a CASPubMedWeb of Science®Google Scholar 3jK. A. Nielsen, J. O. Jeppesen, E. Levillain, J. Becher, Angew. Chem. 2003, 115, 197; 10.1002/ange.200390042 Google ScholarAngew. Chem. Int. Ed. 2003, 42, 187; for a review, see: 10.1002/anie.200390074 CASPubMedWeb of Science®Google Scholar 3kJ. O. Jeppesen, J. Becher, Eur. J. Org. Chem. 2003, 3245. Uracil-fused: 10.1002/ejoc.200300078 CASWeb of Science®Google Scholar 3lO. Neilands, S. Belyakov, V. Tilika, A. Edzina, J. Chem. Soc. Chem. Commun. 1995, 325; 10.1039/C39950000325 CASWeb of Science®Google Scholar 3mO. Neilands, V. Liepinsh, B. Turovska, Org. Lett. 1999, 1, 2065; 10.1021/ol9910868 CASWeb of Science®Google Scholar 3nK. Balodis, S. Khasanov, C. Chong, M. Maesato, H. Yamochi, G. Saito, O. Neilands, Synth. Met. 2003, 133–134, 353. 10.1016/S0379-6779(02)00307-7 CASWeb of Science®Google Scholar 4 4aT. Akutagawa, G. Saito, Bull. Chem. Soc. Jpn. 1995, 68, 1753; 10.1246/bcsj.68.1753 CASWeb of Science®Google Scholar 4bT. Akutagawa, G. Saito, M. Kusunoki, K. Sakaguchi, Bull. Chem. Soc. Jpn. 1996, 69, 2487. 10.1246/bcsj.69.2487 CASWeb of Science®Google Scholar 5 5aM. Tadokoro, H. Kanno, T. Kitajima, H. S. Umemoto, N. Nakanishi, K. Isobe, K. Nakasuji, Proc. Natl. Acad. Sci. USA 2002, 99, 4950; 10.1073/pnas.072661699 CASPubMedWeb of Science®Google Scholar 5bY. Morita, T. Murata, K. Fukui, M. Tadokoro, K. Sato, D. Shiomi, T. Takui, K. Nakasuji, Chem. Lett. 2004, 33, 188. 10.1246/cl.2004.188 CASWeb of Science®Google Scholar 6Y. Morita, T. Murata, H. Yamochi, G. Saito, K. Nakasuji, Synth. Met. 2003, 135–136, 579. See also the Supporting Information. 10.1016/S0379-6779(02)00739-7 CASWeb of Science®Google Scholar 7TTF-CHL is a neutral CT complex with 1:1 component ratio and is a semiconductor with low electrical conductivity (σrt=∼10−4 S cm−1): J. B. Torrance, J. J. Mayerle, V. Y. Lee, K. Bechgaard, J. Am. Chem. Soc. 1979, 101, 4747. 10.1021/ja00510a061 CASWeb of Science®Google Scholar 8Crystal data for TTF-Im: C9H6N2S4, Mr=270.40, crystal dimensions 0.25×0.15×0.05 mm3, orthorhombic, space group Pna21 (no. 33), a=10.198(1), b=25.196(4), c=4.1681(5) Å, V=1071.0(2) Å3, Z=4, ρcalcd=1.677 g cm−3, μ=8.49 cm−1, 2 θmax=55.0°, λ(MoKα)=0.71075 Å, ω scan mode, T=200 K, 9749 reflections, of which 2853 were unique and 2116 were included in the refinement [I>2.00 σ(I)], data corrected for Lorentzian and polarization effects; an empirical absorption correction resulted in transmission factors ranging from 0.8302 to 0.9582, solution by direct methods (MITHRIL 90) and refinement on |F2| by full-matrix least-squares procedures (SHELXL97), 136 parameters, the non-H atoms were refined anisotropically, H atoms were included but not refined, final values R1=0.032, wR2=0.069, GOF=1.06, maximum positive and negative peaks in ΔF map were ρmax=0.26 e Å−3 and ρmin=−0.21 e Å−3. CCDC-239640 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or [email protected]). Google Scholar 9 9aS. Martinez-Carrera, Acta Crystallogr. 1966, 20, 783; 10.1107/S0365110X66001853 CASWeb of Science®Google Scholar 9bB. M. Craven, R. K. McMullan, J. D. Bell, H. C. Freeman, Acta Crystallogr. Sect. B 1977, 33, 2585. 10.1107/S0567740877008954 Web of Science®Google Scholar 10Crystal data for (TTF-Im)2(CHL): C12H6N2OS4Cl2, Mr=393.34, crystal dimensions 0.30×0.05×0.02 mm3, triclinic, space group P (no. 2), a=3.7573(2), b=12.2435(4), c=15.8037(5) Å, α=93.996(3), β=85.915(3), χ=82.138(3)°, V=716.02(5) Å3, Z=2, ρcalcd=1.824 g cm−3, μ=95.20 cm−1, 2 θmax=55.0°, λ(CuKα)=1.54178 Å, ω scan mode, T=293 K, 8786 reflections, of which 2521 were unique and 7895 were included in the refinement [I>2.00 σ(I)], data corrected for Lorentzian and polarization effects; an empirical absorption correction resulted in transmission factors ranging from 0.7196 to 1.0000, solutions by direct methods (SIR 97) and refinement on |F2| by full-matrix least-squares procedures, 192 parameters, the non-H atoms were refined anisotropically, H atoms were included but not refined, final values R1=0.058, wR2=0.171, GOF=1.068, maximum positive and negative peaks in ΔF map were ρmax=0.42 e Å−3 and ρmin=−0.42 e Å−3. CCDC 239641 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or [email protected]). Google Scholar 11Selected physical data: (TTF-Im)2(CHL), IR (KBr): =3200–2700, 1532 cm−1; UV/Vis (KBr): λmax=290, 386, 700, 834 nm; elemental analysis (%): calcd for (C9H6N2S4)2(C6O2Cl4): C 36.64, H 1.54, N 7.12; found: C 36.77, H 1.57, N 7.22. Google Scholar 12A. Girlando, I. Zanon, R. Bozio, C. Pecile, J. Chem. Phys. 1978, 68, 22. 10.1063/1.435487 CASWeb of Science®Google Scholar 13(TTF-Im)2(CHL) shows the lower-energy absorption band at around 3000 cm−1, which is characteristic of partial CT complexes with segregated stacking columns (see the Supporting Information). Google Scholar 14The oxidation potential of TTF-based donor molecules with an amido moiety is strongly affected by formation of H-bonds to inorganic anions.[3c] Google Scholar 15Calculation method: T. Mori, A. Kobayashi, Y. Sasaki, H. Kobayashi, G. Saito, H. Inokuchi, Bull. Chem. Soc. Jpn. 1984, 57, 627. 10.1246/bcsj.57.627 CASPubMedWeb of Science®Google Scholar 16The amount of the temperature-dependent contribution, 1.1 %, was determined by the saturation magnetization at 1.9 K (123.01 erg Oe−1 mol−1) under the assumption that a unit of (TTF-Im)2(CHL) has nominally two S=1/2 spins by complexation. Google Scholar 17The ESR spectra observed at all temperatures were reproduced by spectral simulation for a randomly oriented system, which assumes temperature-independent g anisotropy (see text) and temperature-dependent peak-to-peak linewidths (inset of Figure 5). Google Scholar 18The 2 J value was calculated at the UB3LYP/6-31G(d) level according to the procedure developed by Yamaguchi et al.: Y. Takano, T. Taniguchi, H. Isobe, T. Kubo, Y. Morita, K. Yamamoto, K. Nakasuji, T. Takui, K. Yamaguchi, J. Am. Chem. Soc. 2002, 124, 11 122, and references therein. 10.1021/ja0177197 CASWeb of Science®Google Scholar 19J. C. Bonner, M. E. Fisher, Phys. Rev. A 1964, 135, 640. 10.1103/PhysRev.135.A640 Web of Science®Google Scholar 20R. P. Groff, A. Suna, R. E. Merrifield, Phys. Rev. Lett. 1974, 33, 418. 10.1103/PhysRevLett.33.418 CASWeb of Science®Google Scholar 21A phase transition in H-bonded CT complex: K. Nakasuji, K. Sugiura, T. Kitagawa, J. Toyoda, H. Okamoto, K. Okaniwa, T. Mitani, H. Yamamoto, I. Murata, A. Kawamoto, J. Tanaka, J. Am. Chem. Soc. 1991, 113, 1862. 10.1021/ja00005a078 CASWeb of Science®Google Scholar Citing Literature Volume43, Issue46November 26, 2004Pages 6343-6346 ReferencesRelatedInformation
Publication Year: 2004
Publication Date: 2004-11-23
Language: en
Type: article
Indexed In: ['crossref', 'pubmed']
Access and Citation
Cited By Count: 101
AI Researcher Chatbot
Get quick answers to your questions about the article from our AI researcher chatbot