Single-Component Charge-Transfer Crystals Based on Spin-Carrying TCNQ (7,7,8,8-Tetracyanoquinodimethane) Derivatives
Abstract
:1. Introduction
2. Results and Discussion
2.1. Preparation and Redox Properties of TCNQ Derivatives Carrying Nitroxide Substituents (3a–3c)
Compound | E1RED | E2RED | E1OX |
---|---|---|---|
3a | 0.03 | −0.44 | 0.75 |
3b | 0.04 | −0.43 | 0.84 |
3c | 0.02 | −0.42 | 0.92 |
2 | 0.04 | −0.41 |
2.2. Crystal Structures and Magnetic Properties of TCNQ Derivatives Carrying Nitroxide Substituents (3a–3c)
compound | magnetic interaction a | C b/emu K·mol−1 | |
---|---|---|---|
3a | antiferromagnetic | 0.75 (100) | −1.20 |
3b | antiferromagnetic | 0.68 (91) | −1.40 |
3c | antiferromagnetic | 0.59 (79) | −1.10 |
3. Experimental Section
3.1. Materials
3.3. Preparation and Crystal Data of TCNQ Derivative 3a
4. Conclusions
Conflict of Interest
References
- Ferraris, J.; Cowan, D.O.; Walatka, V., Jr.; Perlstein, J.H. Electron transfer in a new highly conducting donor-acceptor complex. J. Am. Chem. Soc. 1973, 95, 948–949. [Google Scholar] [CrossRef]
- Kobayashi, A.; Tanaka, H.; Kumasaki, M.; Torii, H.; Narymbetov, B.; Adachi, T. Origin of the High Electrical Conductivity of Neutral [Ni(ptdt)2] (ptdt = propylenedithiotetrathiafulvalene- dithiolate): A Route to Neutral Molecular Metal. J. Am. Chem. Soc. 1999, 121, 10763–10771. [Google Scholar] [CrossRef]
- Zhou, B.; Yajima, H.; Idobata, Y.; Kobayashi, A.; Kobayashi, T.; Nishibori, E.; Sawa, H.; Konayashi, H. Single Component Layered Molecular Conductor, [Au(ptdt)2]. Chem. Lett. 2012, 41, 154–156. [Google Scholar] [CrossRef]
- Kobayashi, A.; Fujiwara, E.; Kobayashi, H. Single-Component Molecular Metals with Extended-TTF Dithiolate Ligands. Chem. Rev. 2004, 104, 5243–5264. [Google Scholar] [CrossRef]
- Belo, D.; Alves, H.; Lopes, E.B.; Duarte, M.T.; Gama, V.; Henrique, R.T.; Almeida, M.; Pérez-Benítez, A.; Rovira, C.; Veciana, J. Gold Complexes with DithiothiopheneLigands: A Metal Based on a Neutral Molecule. Chem. Eur. J. 2001, 7, 511–519. [Google Scholar] [CrossRef]
- Nunes, J.P.M.; Figueira, M.J.; Belo, D.; Alves, H.; Santos, I.C.; Ribeiro, B.; Lpes, E.B.; Henrique, R.T.; Vidal-Gancedo, J.; Veciana, J.; Rovira, C.; Almeida, M. Transition Metal Bisdithiolene Complexes Based on Extended Ligands with Fused Tetrathiafulvalene and Thiophene Moieties: New Single-Component Molecular Metals. Chem. Eur. J. 2007, 13, 9841–9849. [Google Scholar]
- Tenn, N.; Belleç, N.; Jeannin, O.; Piekara-Sady, L.; Auban-Senzier, P.; Íñiguez, J.; Canadell, E.; Lorcy, D. A Single-Component Molecular Metal Based on a ThiazoleDithiolate Gold Complex. J. Am. Chem. Soc. 2009, 131, 16961–16967. [Google Scholar]
- Nakatsuji, S.; Nobusawa, M.; Suzuki, H.; Akutsu, H.; Yamada, J. Spin-Carrying Benzoquinone Derivatives. J. Org. Chem. 2009, 74, 9345–9350. [Google Scholar] [CrossRef]
- Nakatsuji, S.; Takai, A.; Nishikawa, K.; Morimoto, Y.; Yasuoka, N.; Suzuki, K.; Enoki, T.; Anzai, H. CT complexes based on TEMPO radicals. J. Mater. Chem. 1999, 9, 1747–1754. [Google Scholar] [CrossRef]
- Nakatsuji, S.; Amano, T.; Akutsu, H.; Yamada, J. Organic biradical compounds with a mesogenic core and long alkoxy groups: preparation, structures and magnetic properties. J. Phys. Org. Chem. 2006, 19, 333–340. [Google Scholar]
- Akutsu, H.; Yamashita, S.; Yamada, J.; Nakatsuji, S.; Hosokoshi, Y.; Turner, S.S. A Purely Organic Paramagnetic Metal, κ-β′′-(BEDT-TTF)2(PO-CONHC2H4SO3), Where PO = 2,2,5,5-Tetramethyl -3-pyrrolin-1-oxyl Free Radical. Chem. Mater. 2011, 23, 762–764. [Google Scholar] [CrossRef]
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Suzuki, H.; Akutsu, H.; Yamada, J.-i.; Nakatsuji, S. Single-Component Charge-Transfer Crystals Based on Spin-Carrying TCNQ (7,7,8,8-Tetracyanoquinodimethane) Derivatives. Crystals 2012, 2, 662-668. https://doi.org/10.3390/cryst2020662
Suzuki H, Akutsu H, Yamada J-i, Nakatsuji S. Single-Component Charge-Transfer Crystals Based on Spin-Carrying TCNQ (7,7,8,8-Tetracyanoquinodimethane) Derivatives. Crystals. 2012; 2(2):662-668. https://doi.org/10.3390/cryst2020662
Chicago/Turabian StyleSuzuki, Hideto, Hiroki Akutsu, Jun-ichi Yamada, and Shin’ichi Nakatsuji. 2012. "Single-Component Charge-Transfer Crystals Based on Spin-Carrying TCNQ (7,7,8,8-Tetracyanoquinodimethane) Derivatives" Crystals 2, no. 2: 662-668. https://doi.org/10.3390/cryst2020662