The first BETS radical cation salts with dicyanamide anion: Crystal growth, structure and conductivity study

Kushch, N. D.; Buravov, L. I.; Chekhlov, A. N.; Spitsina, N. G.; Kushch, P. P.; Yagubskii, Eduard B.; Herdtweck, Eberhardt; Kobayashi, Akiko

doi:10.1016/j.jssc.2011.09.001

Cited by 4 publications

(14 citation statements)

References 25 publications

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“…The crystal structure of κ-(BETS) 2 complex salt as electrolyte following the procedure reported in Reference [19]. 13 C-enriched (>99%) BETS ( Figure 1b) was synthesized with the use of 13 C-enriched triphosgene (bis(trichloromethyl-13 C 3 )carbonate) according to the method described in literature [20].…”

Section: Methodsmentioning

confidence: 99%

Properties of Mn2+ and Π-Electron Spin Systems Probed by 1H and 13C NMR in the Organic Conductor κ-(BETS)2Mn[N(CN)2]3

et al. 2012

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Properties of the spin systems of the localized 3d Mn 2+ ions and the conduction π electrons in quasi-two-dimensional organic conductor κ-(BETS) 2 Mn[N(CN) 2 ] 3 were accessed using 1 H and 13 C NMR in order to find their relation to the metal-insulator transition which occurs at ∼23 K. The transition of the system into the insulating state is shown to be followed by localization of the π spins into a long-range ordered staggered structure of AF type. In contrast, the 3d Mn 2+ electron spin moments form a disordered tilted structure, which may signify their trend to AF order, frustrated geometrically by the triangular arrangement of Mn in the anion layer. This result suggests that the MI transition in κ-(BETS) 2 Mn[N(CN) 2 ] 3 is not the consequence of the interactions within the Mn 2+ spins but due to the interactions within the π-electron system itself. Vice versa, it is more likely that the disordered tilted structure of the Mn 2+ spins is induced by the ordered π-spins via the π-d interaction.

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Section: Methodsmentioning

confidence: 99%

Properties of Mn2+ and Π-Electron Spin Systems Probed by 1H and 13C NMR in the Organic Conductor κ-(BETS)2Mn[N(CN)2]3

et al. 2012

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“…1 [12]. In this paper we report the results of 13 C NMR experiments on BETS-Mn performed at ambient pressure and under an external pressure sufficient to suppress the MI transition.…”

Section: Much Effort Has Been Done Recently To Understand the Influen...mentioning

confidence: 99%

“…The sample was a single crystal of BETS-Mn with BETS molecules containing (at least) 99% of 13 C isotope in the positions of the central carbons, Fig. 1.…”

Section: Much Effort Has Been Done Recently To Understand the Influen...mentioning

confidence: 99%

“…BETS-Mn crystals were synthesized by electrochemical oxidation of the 13 C-labeled BETS in the presence of the complex salt Ph 4 PMn[N(CN) 2 ] 3 as electrolyte according to the procedure described in Ref. 13. The sample was suspended inside a 5 × 5 × 0.5 mm 3 NMR rf coil on four 10 µm-thick platinum leads attached to the sample to provide the resistivity measurements across the conducting (b, c) plane, and sealed inside a PTFE can.…”

Section: Much Effort Has Been Done Recently To Understand the Influen...mentioning

confidence: 99%

“…For the experimental geometry of our choice, H⊥[0 11], (H, a * ) = 45 • , the 13 C NMR spectrum measured in the metallic state of the title compound is a single resonance line, as exemplified in Figure 3(c). In theory, for the given field orientation one expects a BETS-Mn crystal to produce four 13 C NMR peaks [15]. They arise from the two magnetically different orientations of the BETS dimers in the unit cell, as shown in Fig.…”

Section: Much Effort Has Been Done Recently To Understand the Influen...mentioning

confidence: 99%

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Staggered spin order of localized π-electrons in the insulating state of the organic conductor κ-(BETS)2Mn[N(CN)2]3

et al. 2012

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Magnetic properties of the conduction π-electron system of κ-(BETS) 2 Mn[N(CN) 2 ] 3 have been probed using 13 C NMR. At ambient pressure, the metal-insulator transition observed in the resistivity measurements below T ≃ 23 K is shown to be accompanied by ordering of the π-spins in a long-range staggered structure. As the metal-insulator transition is suppressed by applying a small pressure of ∼ 0.5 kbar, the π spin system maintains the properties of the metallic state down to 5 K. PACS numbers: 74.70.Kn, 71.30.+h, 76.60.Jx 1 The organic charge-transfer salt κ-(BETS) 2 Mn[N(CN) 2 ] 3 [1] (hereafter abbreviated as BETS-Mn) is a quasi-two-dimensional metal consisting of insulating layers of Mn[N(CN) 2 ] − 3 polymer anions alternating with conducting layers of dimers of organic radical cations BETS[bis(ethylenedithio)tetra-selenafulvalene, C 10 S 4 Se 4 H 8 ] molecules (Fig. 1). The bulk magnetic properties of the system are dominated by the paramagnetic 3d electron spin moments of Mn 2+ ions (S d = 5/2, g ≈ 2) located in the anion layers [1,2]. The (BETS) + 2 dimers accommodating one hole per dimer, form an effectively half-filled quasi-two-dimensional πelectron conduction band [3]. The compound undergoes a metal-insulator (MI) transition at cooling below T MI ∼ 23 K at ambient pressure [1]. The transition temperature rapidly decreases at applying pressure, P , so that at P ≥ 1 kbar the system is metallic in the whole temperature range [3]. Moreover, it goes superconducting with maximum T c = 5.8 K at P = 0.6 -1.0 kbar.Much effort has been done recently to understand the influence of paramagnetic d-metal ions of the anion layers on the transport properties of quasi-two-dimensional systems [4,5].It has been undoubtedly established now that the field-induced superconductivity in λ-(BETS) 2 FeCl 4 and κ-(BETS) 2 FeBr 4 arises when the external magnetic field compensates the exchange field created by localized 3d moments of Fe 3+ on the spins of itinerant πelectrons [6]. The role of π-d interactions in driving the MI transition observed in the systems with magnetic anions is not as clear. For example, at ambient pressure and zero field, non-magnetic (BETS) 2 Ga(Cl,Br) 4 systems are metallic down to lowest temperatures, whereas the iron-containing κ-(BETS) 2 Fe(Cl,Br) 4 are metallic below the antiferromagnetic (AF) transition, and λ-(BETS) 2 FeCl 4 is a uniaxial Néel-type AF insulator below T N = T MI = 8 K [5]. It has been suggested [7] that in the abovementioned Fe-containing systems the AF state is initiated within the system of 3d electron spin moments of Fe 3+ ions, which in the case of λ-(BETS) 2 FeCl 4 drives the MI transition as well. This reasonable assumption has been doubted however in later communications [8,9].Despite the similarity of the title compound to the listed systems with FeX 4 (X=Cl, Br) anions, including the presence of the 3d ions in the anion layer and the MI transition, its phase diagram is different. First, at ambient pressure the system remains insulating in the external magnetic field up to...

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Synthesis particularities, structure and properties of the radical cation salts ω-(BEDT-TTF)5M(SCN)6·C2H5OH, M=Mn, Ni

et al. 2014

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The first BETS radical cation salts with dicyanamide anion: Crystal growth, structure and conductivity study

Cited by 4 publications

References 25 publications

Properties of Mn2+ and Π-Electron Spin Systems Probed by 1H and 13C NMR in the Organic Conductor κ-(BETS)2Mn[N(CN)2]3

Properties of Mn2+ and Π-Electron Spin Systems Probed by 1H and 13C NMR in the Organic Conductor κ-(BETS)2Mn[N(CN)2]3

Staggered spin order of localized π-electrons in the insulating state of the organic conductor κ-(BETS)2Mn[N(CN)2]3

Synthesis particularities, structure and properties of the radical cation salts ω-(BEDT-TTF)5M(SCN)6·C2H5OH, M=Mn, Ni

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