1:2 TCNQ/TCNQ−. mixed salts exhibiting ferromagnetic behavior at room temperature

Ueda, Kazuyuki; Sugimoto, Toyonari; Endo, Satoshi; Toyota, Naoki; Kohama, Masakado; Yamamoto, Kōji; Suenaga, Yusaku; Morimoto, Hiroshi; Yamaguchi, Toshiyuki; Munakata, Megumu; Hosoito, Nobuyoshi; Kanehisa, Nobuko; Shibamoto, Yoshiyuki

doi:10.1016/0009-2614(96)00982-7

Cited by 31 publications

(14 citation statements)

References 9 publications

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“…The TCNQ salts with inorganic cations evoke, as paramagnetic units, a remarkable interest too [7,8]. It was shown, for instance, that 1:2 TCNQ/TCNQ À mixed salts exhibit ferromagnetic behaviour at room temperature [9]. The TCNQ derivatives containing electron-donor groups appeared recently of great importance when looking for the new materials to be applied [10,11].…”

Section: Introductionmentioning

confidence: 99%

Inelastic neutron scattering (INS) spectrum of tetracyanoquinodimethane (TCNQ)

Pawlukojć

Natkaniec

Bator

et al. 2003

Chemical Physics Letters

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Section: Introductionmentioning

confidence: 99%

Inelastic neutron scattering (INS) spectrum of tetracyanoquinodimethane (TCNQ)

Pawlukojć

Natkaniec

Bator

et al. 2003

Chemical Physics Letters

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“…[1][2][3][4][5][6] These novel properties are related, in part, to a propensity to form diverse structural arrangements that vary with the size, identity, and shape of the counter-cation or synthetic reaction conditions. Infinite 'equidistant' stacks of TCNQ or repetition of stacks composed of dimers, trimers, tetramers, and even pentamers [1,[7][8][9][10][11][12][13][14][15] are often features that facilitate high electronic conductivity and even metallic behaviour, [1,16] e.g. TTF-TCNQ (where TTF is tetrathiofulvalene).…”

Section: Introductionmentioning

confidence: 99%

Structural, Spectroscopic, and Electrochemical Characterization of Semi-Conducting, Solvated [Pt(NH3)4](TCNQ)2·(DMF)2 and Non-Solvated [Pt(NH3)4](TCNQ)2

Nafady

Abrahams

et al. 2017

Aust. J. Chem.

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The demand for catalysts that are highly active and stable for electron-transfer reactions has been boosted by the discovery that [Pt(NH3)4](TCNQF4)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) is an efficient catalyst. In this work, we prepare and characterize the two related [Pt(NH3)4]2+ complexes, [Pt(NH3)4](TCNQ)2·(DMF)2 (1) and [Pt(NH3)4](TCNQ)2 (2). Reaction of [Pt(NH3)4](NO3)2 with LiTCNQ in a mixed solvent (methanol/dimethylformamide, 4 : 1 v/v) gives [Pt(NH3)4](TCNQ)2·(DMF)2 (1), whereas the same reaction in water affords [Pt(NH3)4](TCNQ)2 (2). 2 has been previously reported. Both 1 and 2 have now been characterized by single-crystal X-ray crystallography, Fourier-transform (FT)IR, Raman and UV-vis spectroscopy, and electrochemistry. Structurally, in 1, the TCNQ1− anions form infinite stacks with a separation between adjacent anions within the stack alternating between 3.12 and 3.42 Å. The solvated structure 1 differs from the non-solvated form 2 in that pairs of TCNQ1− anions are clearly displaced from each other. The conductivities of pressed pellets of 1 and 2 are both in the semi-conducting range at room temperature. 2 can be electrochemically synthesized by reduction of a TCNQ-modified electrode in contact with an aqueous solution of [Pt(NH3)4](NO3)2 via a nucleation growth mechanism. Interestingly, we discovered that 1 and 2 are not catalysts for the ferricyanide and thiosulfate reaction. Li+ and tetraalkylammonium salts of TCNQ1−/2− and TCNQF41−/2− were tested for potential catalytic activity towards ferricyanide and thiosulfate. Only TCNQF41−/2− salts were active, suggesting that the dianion redox level needs to be accessible for efficient catalytic activity and explaining why 1 and 2 are not good catalysts. Importantly, the origin of the catalytic activity of the highly active [Pt(NH3)4](TCNQF4)2 catalyst is now understood, enabling other families of catalysts to be developed for important electron-transfer reactions.

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“…Introduction (NMe 4 ) 2 TCNQ 3 and Cs 2 TCNQ 3 belong to the TCNQ based cation/anion 2 : 3 compounds [1,2]. Their crystals consist of TCNQ/TCNQ -and donor molecules or atoms stacked along the b-axis of the monoclinic structure.…”

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confidence: 99%

“…1. Introduction (NMe 4 ) 2 TCNQ 3 and Cs 2 TCNQ 3 belong to the TCNQ based cation/anion 2:3 compounds [1,2]. Their crystals consist of TCNQ/TCNQ -.…”

mentioning

confidence: 99%

“…molecules conform a slipped dimer in which they are displaced against each other in the direction of the short molecular axis. Despite the fractional (0.67) electronic charge per molecule, these two substances are semiconductors with a room temperature conductivity of 6x10 -5 and 2x10 -3 Ω -1 cm -1 , respectively [1]. The low conductivity results from the uneven distribution of the electronic charge along the TCNQ stack [3].…”

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confidence: 99%

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High Pressure Optical Absorption in Organic Semiconductors (NMe4)2TCNQ3 and Cs2TCNQ3

Hasanudin

Kagayama

Kuroda

et al. 2001

phys. stat. sol. (b)

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The pressure dependence of the optical absorption spectrum in (NMe 4 ) 2 TCNQ 3 and Cs 2 TCNQ 3 has been measured at room temperature in the spectral range from mid-infrared to visible. At the ambient pressure the optical energy gap is observed at around 0.5 and 0.3 eV in (NMe 4 ) 2 TCNQ 3 and Cs 2 TCNQ 3 , respectively. The energy gap in (NMe 4 ) 2 TCNQ 3 decreases by 0.05 eV with increasing pressure up to 2 GPa, followed by an abrupt decrease towards 0.2 eV between 2 and 3 GPa. At higher pressures up to 5.5 GPa the gap remains almost unchanged.The intra-and inter-molecular optical absorption bands in the near-infrared to visible region are intensified by pressure and broadened out at 2.5 GPa. The absorption spectrum in Cs 2 TCNQ 3 exhibits a similar behavior under pressure. These results suggest that an electronic phase transition is induced by pressure at around 2.5 GPa in both substances. This phase transition resembles the charge-order-disorder (Verwey) transition in Fe 3 O 4 in the electronic mechanism.

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1:2 TCNQ/TCNQ−. mixed salts exhibiting ferromagnetic behavior at room temperature

Cited by 31 publications

References 9 publications

Inelastic neutron scattering (INS) spectrum of tetracyanoquinodimethane (TCNQ)

Inelastic neutron scattering (INS) spectrum of tetracyanoquinodimethane (TCNQ)

Structural, Spectroscopic, and Electrochemical Characterization of Semi-Conducting, Solvated [Pt(NH3)4](TCNQ)2·(DMF)2 and Non-Solvated [Pt(NH3)4](TCNQ)2

High Pressure Optical Absorption in Organic Semiconductors (NMe4)2TCNQ3 and Cs2TCNQ3

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